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Home , Carbon diselenide, Chromium hexacarbonyl, Cyclopentyne, Disulfur monoxide, Organoactinide chemistry

Advances in

EDITED BY

ROBERT WEST ANTHONY F. HILL

DEPARTMENT OF CHEMISTRY DEPARTMENT OF CHEMISTRY UNIVERSITY OF WISCONSIN IMPERIAL COLLEGE OF SCIENCE, MADISON, WISCONSIN TECHNOLOGY, AND MEDICINE LONDON, ENGLAND

FOUNDING EDITOR

F. GORDON A. STONE

VOLUME 45 Cumulative Subject and Contributor Indexes and Tables of Contents for Volumes 1-44

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A Acetylacetonates, redistribution, 6260 Acetylbis( ~5-cyclopentadieny1)hydndomo- Ab initio calculations Iybdenum, 26337 nonlinear optics, 42311 Acetylcarbonyl-~4--~5- silylenium intermediate, 30245-246 cyclopen tadienylmolybdenum Ab iniiio studies reactions acyclic A5Si-silicates,44:227 with monoxide, 26:344 spirocyclic zwitterionic A%-silicates with conjugated dienes, 26:345-346 with bidentate Iigands thermal rearrangement, 26:342-344 ethene-1,2-diolato(2-), M237-238 with trimethylphosphite, 26:344-345 -2,3-diolato(2-), synthesis, 26337 M232-233 A~etylcarbonyl-~~-cyclopentadienyl-~~- with bidentate -1,2-dio- lato(2-), 44:232-233 dienetungsten complexes diene rotation, 26341-342 Absolute bond energies, definition, 2:108 synthesis, 26:341 Absolute configuration, of chiral metal com- plexes, 18193-195 Acetylcyclopentadienylsodium, tetrahydro- Absolute integrated intensities, v(C0) furan adduct, -224 bands, see Intensities of v(C0) bands Absorption spectroscopy, substituent effects insertion reactions Of, 28:46 in , 40933-135 organic synthesis with nickel carbonyl, Abstraction, hydrogen 841-45 intramolecular, by alkyl radical, M81 q’-Acetylene, formation of titanocene mo- reactivity trends, M79 nocarbonyl complexes, 25358-361 Acetaldehyde Acetylene cobalt carbonyls, inhibition of po- from ethylene, 5321-352 lymerization, 6165 from synthesis gas, 37:202 Acetylene complexes, 1455-57 AcetaIs, formation in 0x0 reaction, 6138 catalytic reactions, 14261-265 Acetate complexes, palladium, nonlability activation of acetylene on coordina- of bridging acetates, 13366-367 tion, 14261-262 Acetates, ally], 28120-121 cocyclization with isocyanides, Acetic acid 14263-265 via carbonylation with com- cyclo-oligomerization, 14262 pounds, 17:233 linear oligomerization, 14:262-263 commercial production, 1R25.5-256 electron-deficient species, 14258-259 Acetohydroximato(2-) bidentate , in Group v metals, lo:% spirocyclic A%-silicates in homogeneous catalysis, 14245-265 NMR studies, M255-256 via insertion reactions, 14251-261 synthesis, a255 geometry of transition state, 14255 Acetonitrile ligand, deprutonation, 18:41 mechanism, 14:253-255 Acetophenone, 26:153 NMR studies, 14251 coupling with Ti-gr, a127 stereochemistry of product, 14251-253 reduction of, 2&102-103 mass spectra, 6291, 301-302

1 Acetylene complexes 2

metalococyclization reactions, 14260-261 metathesis, 16:297 with , 14260 oxidation to benzils or acyloins, 11:193 with isocyanides, 1k260 oxidative-addition reactions, 265-66 metalocyclization reactions, 14256-260 reactions with formation of metalocycloheptatrienes, organotin hydrides, k62-63, 65 14259-260 thiallium(II1) salts, 1k191-194 formation of metalocyclopentadicnes, transition metal carbynes, 2289-94 14:256-257 Acetylene trimerization, catalysis by alkyli- palladium(O), 13375 dynetricobaltnonacarbonyls, 14137 palladium(II), 13374 Acetylenic alcohol, 3248-49 structure and bonding, 14246-2.51 Acetylferrocene, manganesepentacarbonyl effect of metal oxidation statc, 1521 alkyl reaction, 32205 Huckel calculations, 1520-21 Acetylide dianions, 3249 MO scheme, 14246 Acetylide-metal complexes, third-order, nature of interacting orbitals. nonlinear optics, 43377, 379-382, 14246-247 385-387 twisting of C=C bond, 14.56 Acetylide osmium(I1) complexes, variation of CzC bond length. 1456, 29200-201 247 Acetylides, 37:72 variation of CZC-Cn bond angle, bridging, 3266 14247 Acetylmethylenetriphenylphosphorane de- variation of CEC-H bond angle, rivatives, synthesis of, 28234-235 1520-21 3-Acetyl-l-phosphaferrocene, 39345 substitution reactions, 10:352-355 ~3'-r'.4~s-endo-Acetyl-2,2',3-trihydrobis( 1,I ' - cobalt, 10354 cyclopentadieny1)carbonyl-7'- platinum, 10353 cyclopenta-dienylmolybdenum, 26546 thermal stability and extent of back-bond- Acetyltriphenylgermane, structure, 2117 ing, 14248 Acid-base equilibria, organocobalt com- variation in stretching frequencies of pounds, 1k396-397 metal-acetylene unit, 14248-251 Acid halides, reactions with anionic transi- effect of other ligands, 14250 tion metal hydrides, 2241-43 Acetylcnedicobalt hexacarbonyl, Acidic reactions, acyclic hsSi-silicates, 14138-140 44:227-228 analogy with alkyhdynctricobaltnonacar- Acids, hard and soft, activation of C-H bonyls, 14139-140 bonds by transition metal complexes, Acetylenediolate, disodium salt, 185 15148-149 Acetylene-Fe carbonyl complexes, k37-38, Acids, reactions with transition metal car- 41-42 bynes, 2278-81 Acetylenc hydride. 32122 Acoustic frequency, effect on sonochemis- Acetylene oligomerization, catalysis by sup- try, 25237-88 ported nickel complexes, 15224-226 Acoustic intensity, effect on sonochemistry, Acetylene polymerization, cylopentadienylti- 2588 tanium catalysts, 1944 Acrylonitrile, reaction with digermenes, Acetylenes MI38 cocyclization with , 12142 Acrylonitrile complexes, 10143-146 formation of metallocycles, 266 hydrogenation catalyzed by nickel isocya- compounds, 9385-386, nide cluster, 12235. 370 388, 390 hydroplumbation reactions, 228 1 cyclopentadienyls, 9382-39 1 hydrosilation, 12443-445 general chemistry, 9380-382 3 Acyclic pentadienylmetal complexes

organic derivatives, 9382-391 in pentadienyllithium and -potassium Activation of C-H bonds by transition complexes, 26128 metal complexes in ~3-pentadienylmetalcomplexes, in , 15147-185 26141-142 of alkyl groups in polypyrazolylborate cyclization, 26130 compounds, 15157-158 molecular orbitals, 26156-157 in alkyls, 15156-158 orientation by hard and soft acids, 15148-149 in bis(pentadieny1)metal complexes, in ligands, 19149-158 26139 H-D exchange in phosphines, 15149, in cyclopentadienyl(pentadieny1)rho- 154 dium, 26153 orfho-metallation of phosphines, reactions 15149-154 with alkali metals, 26127 Activation parameters with bases, 26127 for carbonyl scrambling with butyllithium, 26127 in ~~-dienechromiumtetracarbonyls, with phenylsodium, 26:127 26304 with potassium amide, 26127 in substituted tricarbonyl(g4-didrene) proton exchange, 26130 complexes, 26307 rearrangements, 26130 in substituted tricarbonyl(v4-diene) structure, 26127-130 tungsten complexes, 26307 bond lengths, 26139 for diene ligand rotation, 26308 bond rotation, 26129-130 for ligand movement, 26320 molecular orbital calculations, 26:129 95 q3 Acyclic (ammonioorgany1)tetrafluorosili- to slippage, 26150 stereoisomerism, 26129 cates, synthesis, M223 Acyclic pentadienylmetal complexes, Acyclic (ammonioorganyl)trifluoro(organyl) 26125-164 silicates, synthesis, 44:223 alkali metal derivatives, preparation, Acyclic diene Fe(C0)3 complexes 26:126-127 cationic configuration, k33 bonding modes, 26125-126 NMR, k12 cross-conjugated dienyltricarbonyliron cat- preparation, k18 , 26:148 Acyclic hydrocarbon ligands, a-bonded, of Group I1 and Group I11 elements, Group 4B carbonyl complexes con- 26130-131 taining, 25372-374 reactions with electrophiles, 26:131-134 Acyclic A’Si-silicates structure, 26131 ab inifio studies, M227 synthesis, 26130-131 acidic reaction, 44:227-228 of Group IV elements, reactions with geometry optimizations, a226 electrophiles, 26134-135 NMR studies, M226-227 reactions physical properties, M227 with alkenyl halides, 26:133 synthesis, M223 with alkyl halides, 26132 Acyclic olefins, catalyzed hydroformylation, with ally1 groups, 26132, 134 17:15-32 with carbonyl groups, 26132-134 by metal carbonyls, 17:15-20 electrophilic attack, 26131-134 by phosphine complexes, 1220-32 group transfer, 26136 Acyclic pentadienyl ligands, 26:126-131 protonation, 26132, 134 acidity, 26126-127 with quinones, 26134 bonding modes, 26126 steric effects, 26132-133 configurations with dioxide, 26:134-135 Acyclic pentadienylmetal complexes 4

transmetallation, 26133-134 reduction with cobalt hydrocarbonyl, with trimethylchlorosilane, 26133 4255 of transition metals, 26:135-158 synthesis, 4245-246 binary pentadienyls, 26135-141 Acyl complexes, 7:189-191 bonding parameters, 26140 from CO insertion reactions, 1k90-104, ligand orientation, 26:139 117-139 molecular structures, 26139-140 kinetics and mechanism of formation, .t)'-pentadienyl complexes, 26:143 1k94-97 .t)'-pentadienyl complexes, 26141-143 ligand effects, 1k90-100 7'-pentadienyl complexes, bonding, effects, 1k97-99 26:156- 158 stereochemistry, 1k112-117 .t)5-pentadienyltricarbonyliroii cations, survey of reactions, 1k117-139 26143-147 Acyl coordinated ligands, electrophilic addi- preparation, X153-155 tion to, 29135-138 Acyclic pcntadienylmetals, anions, Acyldisilancs, silenes from, 3982 26126-131 Acylferrates, for vinylketene synthesis, Acyclic silenes, synthesis. 3976 44324-325 Acyl-alkyl rearrangement, on iridium, Acylgermanes. 2104 1k110 spectral properties, 7: I12 [2-(Acylamino)ethenyl]carbene complexes, synthesis, 2106-107 synthesis, 4k202-203 Acyl group Acylation and ring-mcmber substitution, of dual coordination in osmium cluster, borabenzene metal complexes, 1290 25230-232 reduction to alkyl, 1269-70 Acyl Group IV ketimines, 2135 Acylation reactions, with tricobaltcarbon Acyl halides decacarhonyl cation, 1411 1-1 19 addition to metal complexes, 275-77 Acyl chlorides, catalyzed carbonylation to reaction with beryllium, 9222 ketones, 15224 reduction by organotin hydrides, 1:79, Acylcobalt carbonyls 81-82 formation, 6:123 Acylimines, reaction with disilenes. isomerization, 6:155 39261-262 Acylcobalt tetracarbonyls. 4243-266 Acylimino complexes alcoholysis, 4253-254 from metal alkyls and isoeyanides, cyclization reactions, 4261 -262 11:29-30 derivatives. 4246 protonation, 1139 halogenation, 4256-257 Acylium complexes, 2866 hydrogenation, 4254-255 Acylmetalloids, 198-1 39 insertion reactions, 4258-265 comparisons with ketones, 7:136 acetylenes, 4262-265 photochemistry, 7:126 carbonyl compounds. 4:265 reactions, 2118-130 conjugated dienes, 4260-262 2-(Aeyloxy)alkenyl carbene complexes, syn- olefins, 4258-259 thesis, 4k223-224 isomerization to chelatcd species, Acyl radical, reaction with Sn hydrides, 4246-250 44~96-97 ligand replacement reactions, 4246-253 Acylsilanes, 7100-102, 3981, 89, 93, 106, oxidation. 4256 119 reaction with , reactions, 7:t 18-130 4247-250 hydrolysis, 7:121 kinetics, 4:251 reduction, R119 5 Alcohols

spectra, 7:108-111 organocopper compounds, l2290-301 synthesis, R98-106 , l2:36 hydrolysis of dihalides, 298 S-Adenosylmethionine, biogenic methyl do- oxidation of a-hydroxy compounds, nor, 20315, 338 299 Adiponitrile Acylsilenes, 39:146 via catalyzed hydrodimerization of acrylo- Acyl solvolysis reactions, computer repre- nitrile, 12332 sentation, 26:194 via cyanation of butadiene, 17:224-225 Acylstannanes, 2104 Adsorption preparation, 7:107 alkyl halides on metal surface, 3863-65, spectra, 2112 73 Acyl transfer reactions, corrinoids, 1k425 monomer, Ziegler-Natta catalysis mecha- Acyltris (trimethylsilyl) silane, 3821-22 nism, 18101 Adamantanone, 3840 organotin compounds on surfaces, 'lymSn Addition, see also Cycloaddition Mossbauer spectroscopy, 985 benzene to diphenylketene, 28:16 rhodium carbonyls, onto alumina and sil- by ketenes, 282 ica, 18:257 ketenes to unsaturated organometallic [Ru~(CO)~~]on y-Alz03, 32143 complexes, 282-22 A frame compounds, 3515-19,21,24 anions to chloracetyl chlo- Aggregation, in alkali metal organics, ride, 2828-29 2R178-181 nucleophiles to p carbon by free ketenes, ion size dependence, 22179-181 28.63 solvation dependence, 27:179 in preparation of organometallic 0x0 com- Agostic bonding pounds, 28:342-343 C-H, 30151-154, 183-184 Addition, mechanism, organotin hydrides, Si-H, 30151-154 k63-65, 71 Agostic hydrogen, 26:148-149 1,2 Addition, Grignard, 1:221-223 Agostic species to mesityl ketones, k228-229 characterization, 28:325 to polycyclic ketones, k227 cyclometallation and, 28317 1,3,5 Addition, Grignard, 1:232 definition, 28300 1,4 Addition, Grignard, k221-223 neopentyls, NMR data, 28:322 aromatic-heterocyclic ketones, 1:233-235 recognition by crystallography, mesityl ketones, k228-230 28318-319 to polycyclic ketones, k224 structures, characterized by X-ray meth- quasi-6-membered ring, k224-225 ods, B320 1,6 Addition, Grignard Alcohols Fuchsone type ketones, k231-232 homoallylic, enantioselective synthesis us- mesityl ketones, k228-229,231 ing Sn-gr, 28119 to polycyclic ketones, k228 via hydroformylation, 17:l-57 Addition-elimination reactions, 281 interaction with GIC, 2898 Addition reactions, see also Insertion reac- oxidative carbonylations to dialkyl oxa- tions lates, 28205 l,l-addition, 5230-232. 253-257 reactions with 1,2-addition, 5226-230, 237-253 disilenes, 39:255 1,4-addition, 5227, 230, 237-253 germenes, 44.125 arylpalladium compounds to olefins, lithium silaamidides, 39186-187 13402-409 silenes, 39:133-136 boron-hydrogen bonds to olefins, unsaturated germanium coupounds, 1330-31 39291-292 Alcohols 6

synthesis, oxidation, 38169 back bonding, 2176-177 Alcoholysis from metal carbonyls and acylcobalt tetracarbonyls, 4253-254 anions, 2167-169 alkoxides of molybdenum and tungsten, bases, 2:161-163 27:346-347 reducing agents, 2163-167 carbon-metal bond, 28:184-185 metal-metal bond stability, 2:173 diboranes, 3273 n-bonded ligands, 2172 silane, silicon-oxygcn bond formation, preparation, 2161-169 43248-250 stability factors, 2:172-178 Aldehydes Alkali metals from acid chlorides and silanes, 13323 ate complexes, see ate complexcs, of cucyclization with butadiene, 12146, 176 mixed alkali metal compounds condcnsation with nitromethane, 28101 borinate complexes, rcaction with thalli- via hydroformylation, 121-57 um(1) chloride, 26256 insertion into metal alkyl bonds, 285 n complexes, 26:223-226 by oxidation of olefins, 13370, 378-385 metal-ligand centroid distance, 2k225 reactions of catalytic rcduction, 2244 structures, 26224 reactions with in cyclopentadienyl complexes, anionic transition metal hydrides, 26:125-126 27~41-43 synthesis, 26:127 disilenes, 39:255-256 halides, dimerization energies, 22180 duuhly honded germanium com- organometallic complexes, X-ray struc- pounds, 39:295-296 tural analysis, 27:169-277 compounds, 22118 aggregation, 2R178-181 silenes, 39127 alkyls, 27191-192 reduction with TPPMS complexes, alkynyls, 22194-196 38174- I75 aryls and alkenyls, 27:192-194 Aldol condcnsation, 26:153 benzyl compounds, 27:196-201 Aldol condensation, during hydroforniyla- bond lengths, 22185-190 tion, 122-3, 14 bridging, 27:177-178 Aliphatic organopolysilancs, ki9-110 carbanion structures, without carbon- Alkali metal boratabenzenes metal contacts, 22238-260 Ashe’s synthesis via organotin intermedi- with electron-withdrawing groups, ates, 25217 22238-244 synthesis from bis(boratabenzenc) cobalt enolates, 22254-260 complexes by reductive degradation, radical anions, 27:245 25218 transition metallates, 22246-25 1 Alkali metal carbonylmetallate, reaction charge delocalization, 22171-173 with perfluoroallyl chloride, k183-184 coordination, 22176 with perfluoroacyl halide, kl78-180 cyclooctatetraene compounds, Alkali metal cyclopentadienides 22203-205 from cyclopcntadiene, 2367,369-371 cyclopentadienyl compounds, reaction: with metal carbonyls, 2382 22201-203 with metal salts. 2377-379 graphite intercalates, 22206-208 Alkali metal intercalation compounds ion-dipole complexes, 22236-238 as catalysts, 28107-1 13 ionicity, 22174-176 as reagents, 28:99-107 ligand solvation, 22181-185 synthesis of, 2892-96 mixed-metal compounds, 27:208-235 Alkali metal-metal carhonyls polyphenyl radical anions and polyan- abbreviations, 2160 ions, 22205-206 7 Al kenylsilanes

polyhedrane synthesis, 326-8 mechanisms, 4k143-144 properties, 22174 0x0 ligand migration, 4k144-148 reaction with acyclic pentadienyl ligands, conversion to carbynes, 2264-66 26127 cycloaddition reaction, 22300-306 solvation energies, 22182 hydroformylation, 28199-201 Alkali metal-transition metal n-complexes, hydrohydroxymethylation, 28201 1997-122 hydrosilation, 12407-443 Alkaline earth metals, p complexes, insertion reactions, 5258-277 26236-237 Group I11 elements, 5258-263 p-Alkanediyl complexes, 20161- 162, Group IV elements, 5263-270 237-242 Group V elements, 5270-271 from carbonyl anions and coordinated Group VI elements, 5271-274 ethylene, 20241 transition metals, 5274-277 from w,w’-dihaloalkanes, 20:182, 238 manganesepentacarbonyl alkyl reaction, NMR spectra, 20209, 212 37~199-201 Alkanes metal carbonyl reaction, 37:77 activation by transition metal complexes, metathesis reactions, 22317-319 15147-185 B complexes complexation, 28:326 aluminum, 26241-242 formation during hydroformylation, boron, 26237-238 1212-13 Group VI and VII elements, 26286 oxidation lithium, 26218-220 biochemical, 15149 magnesium, 26232 catalyzed by Co(III), 15182-184 reactions, 38171-172, 174 catalyzed by Mn(III), 15183 reactions with by , 15149 digermenes, M136 via transition metal complexes, disilenes, 39257-258 l5177-184 germenes, 44:126-127 oxidative addition of, 28:317 metal atoms, l559-63 Pt( 11)-catalyzed H- D exchange, nucleophile-carbonyl adducts, 28:178 15165-174 silene, 39114-118 mechanism, 15169-172 synthesis, 32226 nature of catalyst, 15167-169 Alkenoates, metal, thermal decarboxyl- nature of reaction mixture, 15:165-167 ation, 25247-248 relative reactivity of alkanes, Alkenylallenylidene, 3752 15172-174 1-Alkenylboranes, 39:357, 366-367 steric effects, 15173-174 Alkenylcarboranes, reactions, 3322-323 reactions, 38167-170 Alkenyldisilanes, metal-catalyzed redistribu- n-/u-alkyl hi-and trimetallic com- tion, 19230-231 plexes, 32224-235 analogy with olefin metathesis, 19231 n-Alkenelu-carbene bi- and trimetallic com- mechanism, 19230-231 plexes, 37:266-270 Alkenyl esters, hydroformylation, 1242-44 v2-Alkene complexes, electron-transfer reac- up-Alkenyl hydrides, 32226 tions, 2336-37, 60, 78 Alkenyl metal compounds, 337-41 , 3971 Alkenylsilanes, charge transfer complexes bishydroxylation of charge transfer bands, frequencies cycloreversion of rhenium diolates, Of, 34152-154 4k148-156 Iz complexes, 34:153 importance in organic synthesis, IR spectra, M1.52-154 4k142-143 phenol complexes, 34153 Alkenylsilanes 8

T interaction diagram, 34153 mononuclear alkylidyne complexes, 71 orbital conjugation, 34152-153 22320-329 Alkenyl-transition metal complcxes, isomer- reactions ization, 3159-161 metathesis, 22325-327 Al koxides comproportionation reactions, 27:328 multiple bonding, 39:39-44 coordination of Lewis bases, titanium(II1) derivatives, 9:144, 148-149 22327-328 Alkoxides, molybdenum and tungsten hydrolysis. 22328-329 complexes, 22364-365 structure, 22323-325 carbonyl complexes synthesis, 22323-325 carbonyl cleavage reaction, 27:364 by alkyne cleavage, 22321-322 molecular orbitals, 22361 -362 by alkyne metathesis, 22322-323 synthesis, 22359-360 from halides, 22320-321 theoretical studies, 27:360-362 by nitrile cleavage, 22323 dinuclear alkyl and aryl complexes, polynuclear alkylidync complexes, 22344-353 22353-358 alcoholysis, 22346-347 reactions with reactions, 22348-353 alkyncs, 22355-357 with , 22348-351 allene, 27:357-358 cluster formation, 22352-353 carbon monoxide and isonitriles, with phosphines, 22351-352 22358 synthesis, 22344-346 structure, 22353-354 dinuclear alkyne complexes, 22337-344 synthesis, 27:353-355 reactions, 22340-344 Alkoxy( 1 -alkynyl)carbenes. synthetisc alkyne-bond formation, 22340 routes alkyne cleavage, 22342-343 acylation of metallates, 4M68 with nitriles, 22343-344 alkoxy(2-aminoetheny1)carbene com- synthesis and structure, 22337-339 plexes, 41:168 isonitrile adducts, 22362-363 alkoxy(methy1)carbene complexes, 4k167 metallacyclobutadiene complexes, Fischer complexes, 4k166-167 22329-337 Alkoxycarbonylmetal compounds, thermal deprotio derivatives, 22332-333 dccarboxylation, 25265 reactions Alkoxycarbonyls, 8123 alkyne metathesis, 22334-335 characterization of complexes, formation of cyclopentadienyl li- 28:155- 157 gands, 22335-336 decarboxylation, 28184 ring expansion, 22336-337 spectroscopic data, 28151-155 stability, 27:331-332 structural data, 28150-152 structures, 27533-334 synthesis, 28149 synthesis, 22330-333 Alkoxyl alkyl carbene ruthenium(I1) deriva- mononuclear alkylidene complexes, tives, 29183 22312-320 Alkoxyl radical, rcaction with Sn hydrides, reactions a101 alkene metathesis, 22317-319 2-Alkoxy-l-metalla-1,3,5-hexatrienes,cycli- coordination of Lewis basis, 22319 zation reactions, 41:174-175 rearrangement, 27:320 Alkoxymethyl complex, synthesis of nonhet- Wittig reactions, 22319-320 eroatom-substituted Os, Ir and Ru car- spectroscopic data. 22314 bene (alkylidene) complexes from, structure, 22315-316 25160-1 61 synthcsis. 27512-314, 316-317 3-Alkoxy pyrrholes, synthesis, 4k203 9 Alkyl complexes a-Alkoxy radical, reaction with Sn hy- polycyclic oligomer, 3k272 drides, 44:95-96 Alkyl and aryl metal compound Alkoxysilanes amide substitution, 3k270 addition of silenes, 39136-137 Grignard reagent, 3k269 properties, 6:32-34 solvent-induced equilibrium, 31:269 synthesis, 631 stabilization, 3k269-270 P-Alkoxysilanes, 3840 Alkyl arene osmium, from osmium(0) inter- Alkoxysilylketene, 39146-147 mediates, 29198-200 (Alkoxysilyl)lithium, 3819-20 Alkyl (aryl) derivatives of transition metals, cr-AlkyUn-alkene bi- and trimetallic com- 2158-204 plexes, 32224-235 complex anions, 2160-162 cr-Alkylh-alkyne bi- and trimetallic com- synthesis, 2158-167 plexes, 32246-265 from anionic alkylating agents, u-AlkyUa-ally1 bi- and trimetallic com- 7:158-160 plexes, 32235-246 by elimination reactions, 2166-167 Alkylaluminum complexes, alkyl group ex- by insertion reactions, 2165-166 change, 3156 by oxidative-addition reactions, Alkylaluminum dichlorides, 35 2162-164 Alkylaluminums Alkylation adducts with Lewis bases, 8201-202 catalyzed by alkali metal GIC, exchange reactions, 8:179-183 28109-110 intramolecular exchange, 8180-183 of CgK, 2899-100 Alkylamines of ketene complexes, synthetic applica- manganesepentacarbonyl alkyl reaction, tion of, 2&52 32198-199 a-Alkylation, of ketones, via organocopper pharmacological activity of silicon deriva- compounds, n266 tives, 18285-286 Alkylazides, reaction with iminosilanes, Alkyl and aryl complexes, formation, 39176 U15-21 Alkylbenzene, hydrogenation of, a107 by cleavage of Alkylboranes, 39366 carbon-carbon bonds, l219-20 pyrolysis, 2282, 284-287 carbon-hydrogen bonds, 12:18-19 Alkylbromides, 28:101 from complex halides and Grignard re- metal corrosion in seawater, 3871-74 agents, 12.15-18 Alkylchlorides, 28101 from olefin complexes, U20-21 Alkylchromium(II1) complexes, in aqueous Alkyl and aryl metal amide solution, 38156-160 alkaline earth element, 3k270-271 Alkylcobalt carbonyls, isomerization, 6:155 chelating ligand, 3k271 Alkylcobalt complexes, 38108 dimerization, 3k271 Alkylcobalt(II1) complexes, in aqueous solu- substituent effect on structure, 31:271 tion, 38160-162 aluminum, gallium, indium, and thallium, Alkylcobalt tetracarbonyls, 4243-266 3k271-276 carbon monoxide insertion, 4258 boat-chair isomerization, 31:272 isomerization, 4244-245 bond length, 3k272 ligand replacement reactions, 4246-253 bulky substituent effect, 3k272-273 synthesis, 4243-245 cyclic and chelated, 3k273-276 thermal decomposition, 4257 dimeric, 3k273-275 Alkyl complexes formation, 3k271 electron-transfer reactions, 2334-36 macrocycle, 31:276 hydride abstraction reactions, 16:247-248 monomeric, 3k273 I3C NMR spectra, 19263-267 Alkyl complexes 10

CH coupling constants, 19263, cross coupling with a-allylnickel(1) com- 265-266 plex, 26.202-209 substituent effects, 19263-264 hydrolysis, 3871 transition metals, 1x6-10 metal leaching and corrosion, 3871-74 arene molybdenum compounds, nonsynthetic applications, 38:69-74 13: 88 - 9 0 physical properties, 3861 Alkyl compounds reactions with, anionic transition metal alkali metals. 27:191-192, 218-219 hydrides, 2235-41 antimony(\/), 14232-236 reactions with metal, 3859, 61-63, 65-69 arsenic(V), 14229-231 addition of water, 3870-71 indium halides, reaction with triorganos- Direct Process Reaction, 3860, 67-69, tibinc sulfide, 14196 74-75 lithium, in reduction of CICCO~(CO)~, Grignard reaction, 3866-67 14103 reduction with organotin hydride, niobium, 14237-238 1:70-80 phosphorus( V), 14209-224 Wurtz coupling, 28:100-101 tantalum, 14238-239 Alkyl hydrides, 28:330 tin. reaction with tricobaltcarbon decacar- Alkylidene complexes, 32236 bony1 cation, 14115 photochemistry, M327-340 p- zinc, in alkylation of tricobaltcarbon deca- Alkylidene complexes via acetylene insertion, 20219, 222 carbonyl cation, 14115 via hydrogen transfer to m, h*-vinyl, Alkylcopper reagents, cis addition to al- 20193 kynes, l2:229 3-Alkylidenecyclobutenes,1,2-disubstituted, r-AlkyYa-cyclopentadienyl bi- and trimetal- 3245-46 lic complexes, 32275-288 Alkylidenecyclopropanes, ring-opening reac- Alkyldiborane, pyrolysis, 2286 tions, 22283-285 Alkyl exchange, of organoboranes, Alkylidenephosphanes, 39193 2258-261 Alkylidenephosphoranes, reaction with acyl- boron hydrides and boron heterocyclics, metalloids, 2123 2260-261 Alkylidenes trialkoxyborane and boron heterocyclics, formatioii mechanism, 251.58 2260-261 as intermediates in ethylene hydrofor- Alkylgallium complexes, 3952 mylation, 26199, 202-203 Alkylgold complexes, 38108 Alkylidenesilanes, 39194 Alkyl-Group 111 compounds, Lewis base ad- Alkylidene trialkylarsoranes, 14224-228 ducts, 8202-203 Alkylidene trialkylphosphoranes, Alkyl groups 14:209-2 14 adsorbed on metal surface, 3864-65 Alkylidyne-alkylidyne coupling, 3267 displacement by nucleophiles, 2188 Alkylidyne carbaborane anionic salt rearrangement, 39254 dynamic behavior, 3k57-58 transfer, 1310 protonation, 31:84-87 Alkyl halides acid dependent, 3k85 addition to metal complexes, 275-77 hydrochloric acid, 3k86-87 adsorption on metal surfaces, 3863-65, mechanism, 3k85-86 73 tetrafluorboric acid, 3k85-86 alkylchromium(II1) complex synthesis reaction from, 38156-157 general, 3k58 alkylcobalt(II1) complex synthesis from, platinum complex, 31:60-61 38160- 161 rhodium complex, 315-63 11 Alkylidyne metal complexes

ruthenium complex, 3k63-64 anion structure, 35168-169 trimetal compound, 31:60-61 four electron donor, 35158 triphenylphosphinegoId(1) chloride, hyper-cluso cage structure, 35167, 3k59, 61 169-170 structure, 31:57 IR spectroscopy, 35169 synthesis, 3k56 metallocarbaborane cages, 35160, 162, Alkylidyne carbaborane complex 164, 166-169 dynamic behavior, 3k59 molecular structure, 35159 exopolyhedral bonding NMR spectra, 35165, 169 B-H-iron, 3k74 pathways, 35166, 170-172 B-H-metal, 31:63-70 reactivity patterns, 35162 B-H-rhodium, 3k62 structures, 35158, 160-171 di-B-H-metal bond, 3k68-69 X-ray diffraction, 35158-159, 167 isomerism, 32:67-68 exo-nido carbametallaboranes, removal, 31:66 35172-176 exopolyhedral u-boron-transition metal molecular structures, 35174 bond NMR spectra, 35176 indium, 31:76 structures, 35173-175 iron, 3k71-74 Fischer type, 35139 mechanism, 31:71-72 HBF4 EtZprotonations platinum, 31:74-75 bidentate phosphines, 35149-152 ruthenium, 3k70 product formation, 35150-151 substituent effect, 3k70 structures, 35150-151 isomerism, 3k59-60,62 monodentate Lewis bases, 35142-149 Alkylidyne complexes, photochemistry, icosahedral cage framework, 24340-344 35146- 149 Alkylidyne ligands reactivity pattern, 35143-145 alkyne comparison, 3k54 structures, 35143-149 asymmetric spanning, 31:59 X-ray diffraction, 35143-144, 146 bonding scheme, 3154 history, 35137-138 bridging, 3k62 HX protonations, 35152-157 carbaborane isolobal mapping, 3k55 anion structure, 35153 complexing agent, 3k53 rearrangement process, 39154-155 metal centers, see Alkylidyne metal com- structures, 35152, 154-156 plexes synthetic utility, 35156 synthesis lowest unoccupied molecular orbital carbametallaborane, 31:55 (LUMO), 35139-140 dimetal, 3155 MsCchemistry, 35139 polynuclear, 3k54 molybdenum complexes transfer to carbaborane cage, 3k77-84 HBF4 Et20 protonation, 35168-169 iron complex, 3k82 monodentate Lewis bases, isomer equilibrium, 3k81 35145-146 mechanism, 3k77,79-80 HX protonations, 35152-154, 156 molybdenum complex, 3k77 two distinct complex protonation, platinum complex, 31:77-81 35160-161, 163, 165 rhenium, 31:83-84 NMR spectroscopy, 35176-181 rhodium, 31:82-83 boron, 3511,180-181 tungsten-platinum species, 3k53-54 cage-carbon resonances, 35179-180 Alkylidyne metal complexes carbon 13, 35178-180 dimetal compound formation, 35157-172 chemical shift ranges, 35177-178, 181 Alkylidyne metal complexes 12

proton, 351777178 tantalum physical studies IR spectra, 32230 bonding description NMR resonances, 32230 chromium-carbon triple bond, 32242 structural data, 32:220 Cr(CH)CI(CO),, 32242 titanium, M-C bond lengths, 32243 metal-carbon bond lengths, 32243 tungsten Mo(CCH?)($-C,Hi)(CO)Z, 32243 absorption and emission spectra, molecular orbital calculations, 32243 32228 chromium bis-carbyne complexes, 32243 IR spectra, 32230, 232 bis-oxo complexes, 32243 NMR resonances, 32:230, 232 IR spectra, 32:233-240 structural data, 32229 metal atom shielding, 32228 gas-phase, bond energies of, 32229, methylcarhyne Iigdnd, bending of, 242 32242 iridium NMR resonances, 32233-240 IR spectra, 32241 0x0-carbyne complexes, 32243 NMR resonances, 32241 structural data, 32229 iron zinc diazomethane, cocondensation with, diazomethane, cocondensation with, 32242 32229 UV photolysis, 32242 IR spectra, 32229,242 matrix isolation, 32:229, 242 protonation studies, 35139-142 molybdenum r ca ct io n s IR spectra, 32230-233 chromium metal atom shielding, 32:228 2-azaallenylidene complexes, 32:263- NMR resonances, 32:230-233 265, 272,293 structural data, 32229 cthylidyne complexes, 32307 orbitals, 32243 coupling rcactions niobium donor ligands, addition of, IR spectra, 32230 32203-304 NMR resonances. 32230 electronic excitation, 32293-304 osmium electrophile, addition of, 32293-304 IR spectra, 32241 trimethylphosphine, 32294-295 NMR resonances, 32241 electrophiles structural data, 32229 AgCt, 32285 Pt-Co bimetallic surfaces, 32:242 CF~COZH.32279,284,287 rhenium CF~SO~MC,32280 aminocarbyne complex, 32243 CuI, 32285 IR spectra, 32240-241 HBF4, 32277-278,280-281, 284 isocyanide complex, 32243 HC1,32:278-279 NMR resonanccs, 32240-241 HI, 32280 structural data, 32229 Mc~HCCOLH,32287 spectroscopic properties [Me,SSMe]BF4, 32284 absorption and emission spectra, [Me2SSMe]S03CF3,32282 32228 ethylidene tungsten rhenium complex, IR spectra, 32230-241 32:290 NMR resonances, 32228, 230-241 ligand substitution structural studies B acceptor properties, 32268 bond angles, 32228-229 anionic complexes, 32274-276 bond lengths, 32:228-229 2-azaallenylidene, 32272 13 Alkylidyne metal complexes

bispyridine complexes, 32266 Fischer-type carbyne complexes, halide ions, CO substitution by, 32259-260 32266 halo complexes, electrochemical oxi- isocyanide complexes, 32269, 271 dation, 32261 mechanism, 32265-266 iodine oxidation, 32260 metal-carbon triple bond, 32270 Schrock-type alkylidyne complexes, metal complexes, rate comparisons, 32259-260 32:266 trihalometal complexes, 32:260-261 trans halide, 32272-273 photochemistry trimethylphosphine treatment, 2-azallenylidene complexes, 32267-268 32260-261 trimethylphosphite treatment, carbyne complexes, electron transfer 32268-269, 273 reactions of, 32264 manganese, carbyne complexes, 32309 cis-bis(phosphine) complexes, 32263 molybdenum photophysical and photochemical prop- bispyridine-substituted complexes, erties of, 32264 32266-267 rhenium bromo tetracarbonyl complexes, aldylidene complex, 32276-277, 312 32:259 carbyne complex, 32308-310 chlorocarbyne complexes, 32292 tungsten cis-bis(phosphine)-substituted com- alkene complexes, 32304 plexes, 32263-264 methylcarbyne complex, 32299-300 aminocarbyne complex, 32:266, 269- phenylcarbyne complex, 32264, 300 270, 300-301,303 tetracarbonylmetal carbyne com- 2-azallenylidene complexes, 32263, plexes, 32260 293 trihalometal complexes, 32260 benzylidene complex, 32279, 305 triscarboxylate complexes, 32313 biphosphonium carbene complex, trisneopentyl neopentylidyne com- 32291 plexes, 32:286-287 bispicoline phenylcarbyne com- tris(tert-butoxy) complex, 32287 plexes, 32269 2,6-xylylcarbyne complex, 32299 bispyridine-substituted complexes, nucleophiles 32~266-267,283-294 diphenylphosphine, 32:290-291 bromo tetracarbonyl complexes, LiC2BIOHI,,32289 32259 PEt3, 32291 carborane carbyne complex, PMe3, 32291 32279-280 PPN[N02], 32289 chlorocarbyne complexes, 32:292 osmium cis-bis(phosphine)-substituted com- carbyne complex, 32285 plexes, 32263-264 trigonal bipyramidal carbyne com- cyclopropylcarbyne complex, 32264, plex, 32278 294 oxidation and reduction diaminoacetylene complex, 32303 2-azaallenylidene, 32263 diethylaminocarbyne complex, 2-azavinylidene, 32261 32271-272 bromine oxidation, 32259-260 dithiocarbene complex, 32282-284 carbyne complexes, oxidation of, ethylidyne complex, 32:303, 307 32:259-262 picoline-substituted complex, 32305 carbyne into alkylidyne complexes, tetracarbonyl aminocarbyne com- transformation of, 32259 plex, 32267-268 Alkylidyne metal complexes 14

tetracarbonylmetal carbyne com- chromium complexes, 32:245-246 plexes, 32:260 molybdenum complexes, 32245-247 tetrakisisocyanide complexes, 32269, nitrogen-based, 32:245 27 1 trifluoroacetic anhydride, usc of, thiocarbyne complex, 32280-281, 32245-246 291 tungsten complexes, 32245-246 trans-aminocarbyne(iodo)complexes, alkoxycarbene ligands 32280 boron trihalide treatment, trihalometal complexes, 32:260 32:243-244 triscarboxylate complexes, 32313 chromium complexes, 32244 trisneopentyl neopentylidyne com- molybdenum complexes, 32244 plexes, 32286-287 rhenium complexes, 32244 tris(pyrazoly1borate) thiocarbyne tungsten complexes, 32244 complex, 32296-297 aluminum, aminocarbyne complexes, tris(tert-butoxy) complex, 32:287-288 32:255 tristrimethylphosphine complex, carbonyl ligands, 32256 32306 chromium vinylcarbene complex, 32307-308 (bromo)tetracarbonyl complexes, 2,6-xylylcarbyne complex, 32299, 32244 308-309 diphenylaminocarbyne complex, unsaturated organic substrates 32:248 acetonitrile, 32316 (ha1o)tetracarbonyl complexes, alkene tungsten complexes, 32304 32245 alkyne molybdenum complex, iridium, vinylidene hydrido complexes, 32304-305 32250-251 benzylidene complex, 32305-306 iron bisalkylidyne ligands, 32311 p-carbido complex, 32248-249 chromium ethylidyne complexes, 32307 dihalocarbene complex, 32248-249 cyclooctyne, 32:312-313 isocyanide ligands dicarbonyltungsten complexes, aminocarbyne complexes, 32:254-255 32307-308 electrophilic addition to, 32254-255 metathesis reactions, 32311-313, molybdenum complexes, 32255 315-316 rhenium complexes, 32255 molybdenum neopentylidene com- trimethylsilyl rhenium complex, plex, 32306 32:254 picoline-substitutcd complex, 32305 tungsten complexes. 32255 rhenium carbyne complex, metathesis reactions 32308-310 carbon-carbon triple bonds, ruthenium acetylide complex, 32256-251 32311-312 metal-metal triple bonds, 32256-257 terminal acetylenes, 32314-315 steric encumbrance, importance of, tristrimethylphosphine tungsten com- 32258-259 plex, 32306 molybdenum tungsten ethylidyne complexes, acctylide complexes, 32251 32307 aminocarbyne complex, 32255 Schrock type, 35139-140 (bromo) tetracarbonyl complexes, structural formulae, 35136-138 32244 synthesis, 35137-138 butylacetylene complex, 32253-254 acyl ligands carbyne complex, 32251-252; mecha- 15 Alkylidynetricobalt nonacarbonyl complexes

nism, 32252-253; re- two distinct complex protonation, arrangement, 32251-252 35158-165 (halo) tetracarbonyl complexes, X-ray diffraction analysis, 35182-183 32245 Alkylidynetricobalt nonacarbonyl com- silyl-substituted vinyl complexes, plexes, 1497-114 32253 analogy with acetylenedicobalt hexacarbo- trichlorometal complexes, 32:247 nyls, 14138-140 a-vinyl complexes, 32252-253 carbon-functional derivatives, 1497-110 vinylidene (bromo) complex, esters, 14110-112 32253-254 as catalysts, 14137-138 vinylidene complexes, 32251 catalytic hydrogenation of unsaturated de- nickel, aminocarbyne complex, 32251 rivatives, 1497-110 niobium, siloxycarbyne complexes, decomposition reactions, 14135-138 32256, 301 to acetylene complexes, 14135-136 osmium, carbyne complex, 32248 to acetylenes, 14135-136 rhenium, 32:244 with methoxide ion, 14136-137 aminocarbyne complex, 32254 oxidation by ceric ion, 14135-136 benzylcarbyne complex, 32249-250 Hammett cT-constant for CCO,(CO)~ isocyanide complex, 32255 group, 14128 neopentyhdyne complexes, IR spectra of ketone derivatives, 14123 32247-248 mechanism of tantalum, siloxycarbyne complexes, formation, 14101 32256, 301 reactions, 14140-141 tetracarbonylmetal carbyne complexes, preparation of alcohol derivatives, 14119 32245 using triethylsilane, 14121-122 thiocarbonyl ligands, 32256 reduction titanium, neopentylidyne complexes, of ketone derivatives, 14119-122 32248 trichlorometal complexes, 32247 by triethylsilane and trifluoroacetic tungsten acid, 14120 (bromo) tetracarbonyl complexes, by organolithium reagents, 14103 32244 stable carbonium ions from, 14119-134 diphenylaminocarbyne complex, steric hindrance in, 1499, 111 32248 structure, 14:99 (halo) tetracarbonyl complexes, synthesis, 14100-110 32245 from acetylenedicobalt hexacarbonyls, tetracarbonyl carbyne complexes, 14100 32245 via addition to olefinic bonds, thiocarbyne complexes, 32256 14:107-108 trichlorometal complexes, 32247 with arylmercury compounds, trinuclear complexes, 32257-258 14103-106 zinc, aminocarbyne complexes, 32255 from cobalt carbonyl and , tungsten complexes 14101-102 ex0 nido carbametallaboranes, 35172- effects of hydrolysis, 14101 173, 175-176 via Friedel-Crafts reactions, 14106-107 HBF4 Et, 0 protonation, 35165-172 with Group I11 halides, 14109-110 bidentate phosphines, 35150-151 via a-haloalkylmercurials, 14103-106 monodentate Lewis bases, via radical reactions, 14107-108 35143- 149 via substitution at apical carbon atom, HX protonations, 35152-156 14103 Alkylidynetricobalt nonacarbonyl complexes 16

tricobaltcarbon decacarbonyl cation from, Alkylplatinum complexes, 38108 14110-119 Alkylplatinum(II1) complexes, in aqueous Alkyl iodides, 3863, 71-74 solution, 38162-163 Alkyliron complexes, 38108, 110 Alkylplumbonic acids, 2298 Alkyl isocyanides, manganesepentacarbonyl Alkyl radical alkyl reaction, 32198-199 intramolecular hydrogen abstraction, Alkyllanthanides, 9365 M81 Alkyl ligands, coordinated, ketene reactions reactions with Sn hydrides, U90-91, and, 287-8 94-99 Alkyllithium-lithium halide exchange reac- Alkylruthenium complexes, 38108 tions, 8169-170 Alkyls, photochemistry, 24250-326 Alkyllithium reagents, 13:13 Alkylsilyl anions, 38:ll-16, 50 in formation of dibcnzoheterocycles, 0-Alkyl-S-sulfoxylates, 1233 13197 Alkyl sulfonate esters, 28101-102 Alkylmanganese complexes, 38108, 110 Alkyltetraborancs, 3294-295 Alkyl-metal anions. complex, 2176 Alkylthalliuni compounds, group exchange. Alkyl-metal bonds, ketcne insertion and, 8191-193 28:4-5 Alkylthallium(II1) compounds, 1k173-177 Alkyl-metal compounds, 3:21-25 decomposition, 1k175-176 in aqueous solution. 38155-156 Alkyltitanium(II1) compounds, 9171-172 alkylchromium(II1) complexes, Alkyl transfer reactions, 23118-125 38156-160 Alkyl-transition metal complexes, alkylcobalt(I1I) complexes, in aqueous 5125-128 solution, 38160-162 Alkyltungsten complexes, 38108 alkylplatinum(II1) complexes, Alkylzirconium complexes, 38:108-109 38162-163 metal carbonyl complexes, 38:163-164 n-Alkynelu-alkyl hi- and trimetallic com- M-C bond distances, 38105-112 plexes, 32246-265 Alkyl-metal nitrosyls, 7:229 n-Alkynelu-carbene bi- and trimetallic com- Alkyl migration mechanism, 1k113 plexes, 32272-275 Alkyl migration reaction Alkyne clusters, 3267, 121 manganesepentacarbonyl alkyls, Alkyne complexes, 12:6-15 32190-194 bonding, fi6-12 rheniumpentacarbonyl alkyls, 32209-210 "C NMR spectra, 12153, 184 Alkylmolybdenum complexes, 38108 direct "C-'H coupling constants in plat- [2-(A1kyloxy)ethenylJcarbenecomplexes, inum compounds. 12164 synthesis, 4k216-218 of copper, fi228-229 Alkylpalladium complexes, 38108 copper-iridium cluster, 12:285-286 Alkylpentaboranes, properties, 3300-301 copper-iron compound, fi286-287 Alkyl(pentacarbony1) compounds d4 Alkyne complexes manganese group, 32169-214 electrochemistry, 2969-71 diffraction studies, 32177-178 electronic spectra, 2964-68 reactions, 37:183-206, 213 five-coordinate, 2912-14 spectroscopy, 32178-182 TR spectra, 2962-64 structure, 32177-183 internal Mo(I1) and W(1I) bisalkync synthesis, 32171-177 complexes, 2959 rhenium based, 32170-171 internal Mo(I1) and W(I1) monoalkyne reactions, 3R206-213 complexes, 29:47-51 synthesis, 32175-177 terminal Mo(I1) and W(I1) alkyne com- Alkylphosphines, 38:165-166 plexes, 29:44-47 17 Alkynes, reactions

terminal Mo(I1) and W(I1) bisalkyne M(CO)(RC= CR)?, 293-6 complexes, 2958 Mo(I1) alkyne complexes, structures of, NMR spectra, 2944-61 2923-24 E2-Alkyne complexes, propargyl and allenyl bisalkynes, 2932-34 complexes, 3243-45 CpML(RC=CR)X, 2930-32 Alkyne B complexes Mo(CO)(RC=CR)L*XZ, 2924-28 aluminum, 26:241-242 Mo(L)(RCE CR)(B-B),, 2928-30 bonding orbitals, 26241 monoalkyne complex syntheses preparation, 26:241 CpMo( RCE CR)LX, 29:9- 12 beryllium, 26.226 CpW(RC=CR)LX, 299-12 gallium, 26:244-246 M(CO)(RC=CR)L=X,, 296-7 indium, 26248-249 Mo(I1) complexes, 2912-13 p-Alkynedicobalthexacarbonyl complexes, monoanionic, bidentate ligand, 297-9 12325-355 W(I1) complexes, 2912-13 bonding, 12:334-336 reactions in d4 monomers, 2971-92 chemical degradation, L2354-355 W(I1) alkyne complexes, structures of, exchange reactions with alkynes, 29:23-24 12345-346 bisalkyne, 2932-34 IR spectra, 12337 Cp WL( RC- CR)X, 2930-32 mechanism of formation, U:332-334 W( CO)(RCECR)L2X2, 2924-28 preparation, 12:32S-332 W(L)(RC=CR)(B-B),, 2928-30 reactions d4 Alkyne monomers of coordinated alkyne, L23S2-354 molecular orbital description of, 2934-44 reactions with reactions of alkyne ligands in, 2971-92 carbon monoxide, 12340-343 Al kynes excess alkynes, Xk348-352 allenyl complexes, reaction with, 32118- organo-Group V ligands, 12343-345 structures, 12334-337 120, 124 thermal decomposition, n355 allenyl ligands, 37:77-81, 92 Alkyne insertion products, formation, annulation with Fischer carbenes, 29:83-90 44:278-287 Alkyne-iron carbonyl complexes, k37-43 dimerization via radical anions, 15279 Alkyne ligands, four-electron formation from coupling C, ligands, background, 291-3 2918-23 bisalkyne complex syntheses, 2913 hydrogenation, 37:226 of CpM(RC=CR),X, 2916-18 insertion reactions of Mo(RC=CR)~(S~CNE~~)~,2914-16 Group I11 elements, 5258-263 of M(RC=CR),LzX,, 29:14 Group IV elements, 5263-270 of W(RC=CR)2(SZCNEt>)*, 2914-16 Group V elements, 9270-271 d4alkyne complexes Group VI elements, 5271-274 electrochemistry, 2969-71 ligands, in triosmium clusters, dimeriza- electronic spectra, 29:64-68 tion and trimerization, 26:61-63 IR spectra, 29:62-64 manganesepentacarbonyl alkyl reaction, NMR spectra, 29:44-61 32199-201 d4 alkyne monomers, molecular orbital organic, 38102, 133-134 description, 2934-44 polymerizations, transition metal cata- formation from coupling C1 ligands lyzed, 231 -32 PhCSCme, 2922-23 Alkynes, reactions RC=COR’, 2918-20 addition to germenes and digermenes, RNHC=CNHR, 2921-22 39299-300 Alkynes, reactions 18

with alkylcobalt carbonyl complexes, ene product formation, 4k181 12.358 iron complexes, 4k185-186, 228-229 cleavage, in synthesis of tungsten alkox- ligand disengagement by hydrostanna- ides, 22321-322 tion, 41:193 with cobalt carbonyl complexes, metallation and transmetallation, 41:227- 12323-371 229,231-233 with 1,3-ditungstacyclobutadienes, derivatives, 41:182 26105-1 11 polycyclic carbon skeleton synthesis, with mercurycobalt carbonyl complexes, 41:182-183 12355-357 radical addition, 4k192 metal atoms, 1563 reaction with carbon nucleophiles metal carbonyls, structures of products, cross-conjugated metallatriene synthe- 5114-125 sis, 41:177-179 metallo-ring systems, 5120-124 cycloaddition reactions and cyclization non-polymerized ligands, 51 16-120 products, 41:180-183, 185-188 polymerized ligands, 5124-125 1-metalla-1,3-hexadien-5-yne synthesis, metathesis, 2698 41:170-171 in molybdenum and tungsten alkox- 1-metalla-l,3,5-hexatriene synthesis, ides. 22325-327, 334-335 41~171-177 in synthesis of tungsten alkoxides, pyranylidene complex synthesis, 27:322-323 41: 188- 192 of transition metal carbynes, 2290 reaction with nitrogen and phosphorus, with molybdenum and tungsten alkox- nucleophiles, 4k194-195, 197-205, ides, 27:348-351,355-357 207-212, 214-215 oligomerization at dimetal centers, reaction with oxygen and sulfur nucleo- 26154-155 philes, 41:215-225 with phosphasilenes, 39:212-213 synthesis, 41:166-170, 229-233 with tin doubly bonded compounds, Alkynyl-cobalt complexes, W108, Ill 39315 Alkynyl compounds, of alkali metals, with transition mctal complexes, 22194-196.219-220 26154-155 Alkynyldisilanes, photolysis, 1988-92 Alkynetetracobaltdecacarbonyl complexes, Alkynyl-gold complexes, 3889, 108, 111- thermal decomposition, 12.355 113, 119 Alkyne-transition-metal complex, see Alkynyl-iron complexes, 3883-84, 89, 99, Strained cyclic alkyne-transition-metal 104, 108, 110, 115,119-120 complex Alkynyl-lead compounds, 2262 Alkynoates, metal, thermal decarboxyl- Alkynyl ligand, structural trans influences, ation, 25247-248 38:117-120 Alkynylberyllium compounds Alkynyl-manganese complexes, 38:108, 110, complexes, 9209-210,215 114-115 anionic derivatives, 9:241 Alkynyl-metal complexes, 3879,139-140 ether complexes, 9212, 233 bonding, 3880-82 Alkynyl bond, 3880 electron spectroscopy, 3884-88 1-Alkynylboranes, 39357, 366-367 molecular-orbital calculations, 3883-84 v'-Alkynylcarbenes, in vinylketene synthe- Mossbauer spectroscopy, 3889 sis, 44:325-326,328-330 NMR spectroscopy, 38:81, 89 (1-Alkyny1)carbenes photoelectron spectroscopy, 3883-84 acylmetallate synthesis, 4k225-227 vibrational spectroscopy, 38120-139 cyclobutene derivatives, 4k180-181 X-ray crystallography, 3890-120 cyclopentenylidene synthesis, 41:192-193 luminescence, 38:88 19 Allenyl groups

terminal complexes, 3890-99, 103 synthesis, 26:359 Alkynyl-metal congeners, M-C bond Allenic organozinc compounds, addition re- distances, 38115-1 16 actions, a109 Alkynyl-molybdenum complexes, 3885, Allen parameters, metal-carbon bond, 297 100, 108, 115 Allenyl-bridged complexes, structure, Alkynyl-nickel complexes, 38537, 89 3289-90 Alkynyl-palladium complexes, 3887, 89, Allenyl(carbony1) dimer, 3271 108,111 Allenyl complexes, 37:76 Alkynyl-phosphorane ligands, 38114 adduct formation, 32120-123 Alkynyl-platinum complexes, 3887-89, 108, alkali metals, geometry, 22178 111, 113, 117-118, 139 alkynes, reactivity toward, 32124 Alkynyl-ruthenium complexes, 38104-105, binuclear 108, 110-111, 114, 117 NMR, 3297-99 Alkynyl-silicon complexes, 38:lOl-102, 104, structure, 3287-90 116-117 homobinuclear allenyl complexes, Alkynyl-titanium complexes, 3884 3266-67 Alkynyl-tungsten complexes, 3885, 89, 108, homometallic, via carbon-carbon bond 110,112-113 formation, 3264-73 Alkynyl-vanadium complexes, 38:89, 2-isopropyl-1,3-butadien-3-ylligated, 112-113 32124 Alkynyl-zirconium complexes, 38:108-109 ligand dynamics, 32100-107 Allene methylene-bridged cluster, 37:124 cooligomerization with butadiene, 12179 mononuclear oligomerization reactions, 14270 NMR, 3293-97 reactions with tungsten alkoxides, structure, 3283-87 27~357-358 NMR, 37:93-100 synthesis via organocopper compounds, phosphido-bridged, 32117, 122 L2293-294 reaction with alkynes, 32118-120 Allene bridged clusters, structure, 37:87 reactivity, 37:107-124 Allene complexes, 37:47 structure, 3252-95 cyclo-oligomerization reactions, synthesis, 3242-83 14:270-278 tetranuclear, structure, 3R90-93 catalysis by Ni(0) complexes, transition metal allenyl complexes, 14271-277 3245-48 catalysis by rhodium complexes, trimetallic allenyl clusters, 37:67 14277-278 trinuclear kinetic studies, 14273 NMR, 3299-100 role of phosphorus ligands, 14275-277 structure, 3290-93 dissociation of, 14269-270 Allenyl groups effect of coordination on allene bond from alkynes, 3277-81 lengths, 14:267 from allenes, 3273-76 formation, 32107-108 binuclear allenylidenes, 3262-64 in homogeneous catalysis, 14265-278 by carbon-carbon bond formation, 'H NMR studies, 14267 37:64-I3 relative reactivates of Ni, Pd, and Pt com- by carbon-hydrogen activation, 3273-81 plexes, 14:269-270 from dienes, 37:76-77 as source of allenyls, 3273-76 from propargyl ligands, 3253-56 X-ray structural data, 14265-267 from propargyl metal complexes, y-qz*-Alleneoctacarbonyldimanganese 3257-62 structure, 26360 reactions. 32120-124 Allenyl groups 20

transfer reagents, 3262 synthesis via phase transfer catalysis, from transition metal propargylic com- 19204-206 plexes, 3757 $-Ally1 complexes Allenylidene complexes, 3241, 52 electron-transfer reactions, 2337-38, 78 bimetallic, 3262-64 redistribution reactions, 23103-105 hinuclear, 3262-64 n-Ally1 complexes, 371-91 ligand dynamics, 32106-107 arene molybdenum compounds, 1388-90 mononuclear, 37:48-52 "C NMR spectra, Xk1.53-154, 185 synthesis mass spectra, 6284, 300-301 p.-alIenylidene complexes, 4k225-227 of palladium(II), 13375-378 hinuclear compounds, 41:225 from allylic compounds and palladium Allenyl transfer reagents, 3262 salts, 13386-387 Ally1 acetates, Pd-gr-mediated nucleophilic substitution reactions, 10371-378 substitution of, 28:120-121 n, a-rearrangements, 10372 Allyl alcohol, catalyzed isomerization to replacement of allyl groups, 10373 propionaldehyde, 16262-263 n,n-transfer between metals, 10374 s-Ally1 alkali metal complexes, 2:358-360 a-Ally1 complexes n-Allylla-alkyl bi- and trimctallic com- "C NMR spectra, a178 plexes, 32235-246 protonation, 8121 n-Allyl-a-ally1 equilibrium. 832 reaction with sulfur dioxide. l252-56 Allylborancs, 39360, 368-369 n-Ally1 compounds Allyl bridged transition metal complcxes, titanium(III), 9167 2325 , %386 n-Allyl-a-cyclopentadienylpalladium, a-AllyUa-carbene bi- and trimetallic com- reac- tions, 10388-389 plexes, 32270-272 Allyl groups Allyl cations, iron carbonyl complexes, bonding modes in metal complexes, k3-4 26:125-126 n-Allylcobalt tricarbonyl systems, 4260- n complexes of lithium, 26:218 262, 264 oxidative addition of, computer represen- reaction with triphenylphosphine, tation, 26:176 4247-250 reaction with pentadienylmetal com- Allyl complexes, 16228-230 plexes, 26132 allyl rotation, 16:228-230 rearrangements, 26130, 181, 197 bridged dipalladium complexes, Allyl halide reactions 19156-177 with B2C14, 10259 isocyanide insertion, 22:278-279 with iron carbonyls, k34 ' 'C NMR spectra Allylic acetates n-bonded, 19265, 279-290 addition reactions, organocopper com- a-bonded, 19266-267 plexes, Xk294-296 nonrigid behavior, 16:219-221 pseudo-Grignard reactions with, 12220 a into a conversion, 5109 Allylic bromides, reactions with Sn-gr and reaction with , 22:159, aldchydes. 28119 161-163 Allylic chlorides, carbonylation, 38175 u-n rearrangcment Allylic organozinc compounds, addition re- molybdenum, 16244-245 actions, 12:104-109 rhodium, 16245 acetylenic bonds, U:107-108 tungsten, 16244-245 carhonyl groups, 12105-106 uranium, 16:249-250 olefinic bonds, 12.106-107 structure and bonding, 5105-112 a-Allyliron cations, 8122-123, 146 21 Aluminum

Allyliron complexes, 32232 w-Ally1 transition metal complexes, a-Allyliron complexes, 1052 2356-357 Allyl-lead compounds, 2257-258 &Ally1 transition metal complexes, Allyllithium, exchange reactions, 8169 2356-357 Allyllithium-tetrameth y lethylenediamine a-Ally1 transition metal complexes, complex, 26218 2330-356 Allylmetal complexes, u-a conversion, 2195 bonding theory, 2333-335 a-Allylmetal complexes catalytic properties, 2353-355 cationic, 8233 classification, 2357-358 mass spectra, 8:215, 277-278, 281-283 displacement, 2351-352 a-Allylmetal nitrosyl complexes, 2229-230 infra red spectra, 2333 a-Allylnickel bromide, reaction with alkyl preparation, 2:344-350 (aryl) iodides, 283 u-ally1 complex, 2326-327 a-Allylnickel carbonyl halides, coupling re- stability, 2350-351 actions, 830-39 structure, 2330-333 a-Allylnickel complexes, k200 table, 2336-343 carbonylation of allylic compounds, 28 u-Ally1 transition metal complexes, as catalysts 2326-330 for ethylene-butadiene codimerization, definition, 2325 12291-294,298-300,304,307 preparation, 2326 for olefin oligomerization, 12109-1 13 properties, 2327-328 reactions, 2327, 329 as initiators of stereospecific butadiene Allyltrimethylsilane, palladium-catalyzed al- polymerization, 12216-217 lyl cleavage, 19226 insertion of acrylonitrile, 12216 Alumina, support for triosmium cluster cat- via oxidative addition, 12208 alysts, 2663-65 reaction Aluminaindanes, 2297, 300-301 with quinones, 12220-221 Aluminatetralins, 2297, 300 with styrene oxide, 12220 Aluminophosphinimides a-Allylnickel compounds cationic isosteres, 9335-337 in organic synthesis, 829-83 cyclic, 9333 a-Allylnickel(1) halide complex, cross cou- Aluminosiloxanes, 9274 pling to alkyl halide, 26:202-209 cyclic, 9331-333 o-(Ally1oxy)phenyl radical, Arrhenius func- Aluminoxanes, in Ziegler-Natta catalysis, tion, 4477 18140-143 a-Allylpalladium derivatives, 1054, 373-378 Aluminum reactions with Fez(CO)p, 1k374, 377 alkyl and aryl metal amide, 3k271-273 N-Allylsilanamine, 39161 alkyl halides as cocatalysts in ethylene bu- Allylsilanes tadiene codimerization, 17:291-292, elimination reactions, 22285-287 296-297,310-311 as organic synthons, 26:134-135 effect on stereoselectivity, 12302-304 Allylsilanolate anion, 38:20 Lewis acidity, 17:296-297, 302-304 (Allyl)silylcuprate, 3843 alkyls, 1314 Allylstannanes, as organic synthons, alkyls, and enhancement of ruthenium- 26:134-135 catalyzed hydrogenation, 12327 a-Ally1 systems anionic hydride complexes, spectroscopic in 7-membered carbocyclic metal com- properties, 225 plexes, 4357, 359, 364-365 borane complexes, 2k63-66 in 8-membered carbocyclic metal com- cyclic and chelated amide, 3k273-276 plexes, 4370, 378, 382, 384 electron-deficient compounds, 15:239-250 Aluminum 22

heterocarborane, 30106-112 structure and bonding, 16112-113 carbollyl transfer agent, 30:106-108 Aluminum organometallic compounds, commo structure, 30108-112 392-3, 5-6 Lewis base adduct, 30108 Aluminum phosphides, 3926, 30-31 reaction, 30107 Aluminum tetraorganodimetallanes, structures, 30106-11 1 396-13 synthesis, 30108-112 Ambient gas, effect on sonochemistry, lithium complexes 2590 ethyls, 2393-394 Americium, mixed alkali metal compounds, hydrogen-bridged derivatives, 24:438 27:256 imino derivative, 2409-410 Amide derivatives, multiple bonding, mixed alkali metal compounds, 22256 3918-26 multiple bonding, 392 Amides T complexes, 26:241-244 asymmetric hydrogenation with chiral li- alkene and alkyne complexes, gands, 17:357 26241-242 from metal alkyls and isocyanides, 1k29 analogy to carbocations, a257 Amidinium complexes, from and iso- cyclopentadienyl complexes, , 1k45 26:242-243 Amidinium hydrocarbon-containing prod- dicarbollyl complexes. 26243-244 ucts, 3R118 structures, 26242 Amination tcrphcnyl derivatives, 44:23-25 C-0 bond cleavage, allylic alcohols, transition metal complexes, 3947-49 34123 Aluminum alkyls via organonickel compounds, 12239-240 direct synthesis, 6:7 Amine-boranes, steric effects, 11:7 reaction with 1,4-diaza-1,3-, Amine oxides, 9:280-283 21:222-225 coordination compounds, 9:283 reaction with propylene, 68 properties, 9280-281 redistribution, 6214-218 Amines transalkylation with olefins, 1998-99 carbonylations, 28205 Zicglcr-Natta catalysts, 6:lO reactions Aluminum amides, 3918-26 with lithium silaamidides, 39186-187 Aluminum arsenide, 3926, 28 with unsaturated germanium com- Aluminum aryloxides, 394, 39-44, 55 pounds, 39292 Aluminum bisthiolates, 3946 [.-Amino acids, via rhodium complexes of Aluminum compounds, 35282 chiral phosphines, 12340 alkyne insertion, 5239 (Amino)alkylchlorosilanes, 3819 metal carbonyl adducts, 23238-241, 251 Amino( 1-alkynyl) carbenes 256,260-264 bond distances, 4k170 Aluminum halides, reactions with spectroscopy, 41:169 carbene complexes. 1k27 synthesis via isocyano compounds, CICCo?(C0)9, 14116-1 19 4k168-170 cobalt carbonyl, 14110 Aminoazocarboranes, methyl rheniumpenta- Aluminum hydrides carbonyl reaction, 32212 MO calculations, 20297 Aminoberyllium alkyls, 9222-230 reaction with organosilanes, 20283, association, 9224 295-298 complexes, 9:226 Aluminum organocompounds, 1691-106, Aminoborylene complexes, 10167 111-1 29 3-Amino-2-(carbomethoxy)thiophene, rearrangements, 16:Yl-106, 111-129 39:291 23 Antimony

Aminochlorosilane, lithiated, 39165 iridium, 3244 4-Amino-l-chroma-1,3-dienes iron, 3224 NMR, 41~195-197 manganese, 3:213, 221 synthesis, 41:194-195 molybdenum, 3197-198,208,210 Amino derivatives of metal carbonyls, nickel, 3247 10117 rhenium, 3223 with bridging amino groups, 10119 tungsten, 3197-198,208,210 Amino(di-t-butoxy)phenylsilane, 39189 Ammonia 1-Amino-2-ethoxy-4-phosphino naphtha- catalyzed reaction with ethylene, lenes, synthesis, 41:215 19:33-34 Aminofluorosilanes, lithiated, 39180-183 homogeneous dehydrogenation, 1931 (Amin0)ketocarbene complexes, synthesis, reaction with butadiene, 17157-158 4k221-222 synthesis catalyzed by alkali metal GIC, Aminolead compounds, 2289-296 28111-113 ligand exchange, 2294 Ammonia, liquid preparation, 2284 physical properties, 184 protolysis, 2294 reactions with metal carbonyls, 1819-33 reactivity, 7293 base reactions, 18:20-22 4-Amino-l-metalla-1,2,3-butatrienes carbonyl substitution, 1819-20 NMR, 4k195-197 disproportionation, 1820-22 synthesis, 4k194-196 as solvent 4-Amino-1 -metalla-1,3-diene, binuclear com- for metal carbonyl chemistry, 1819-33 pound synthesis, 41:197 for organometallic reactions, 1833-36 2-Amino-1-metalla-1-en-3-ynes 1,2-Anionic rearrangements NMR, 4k195-197 organogermanium compounds, 16:l-31 synthesis, 4k194-195 compounds, 16:l-31 2-Amino-] -metalla-1,3,5-hexatrienes Annulation, alkynes with Fischer carbenes, cyclization reactions, 4k173-174 44,278-287 synthesis, 4k172-173 , reaction with silenes, 39113, 6-Amino-l-metalla-l,3,5-hexatrienes,syn- 115 thesis, 4k172 Anthracene-silene adduct, rearrangement 2-Amino-l-metalla-l,3,5,7-octatr4ene,syn- reaction, 39148-149 thesis, 41:189-190 Anthraquinone, methyl rheniumpentacar- Amino-l-metalla-l,3,5-triene, synthesis, bony1 reaction, 37:207 4k188-189 Antihistamines, 18286 4-Amino-l-rnetalla-l-yne-3-ene, synthesis, silyl derivatives, 18287 41:229 Antiladder polygermanes, 37:12, 14 [(Amino)] phenylsilyl] lithium, 3817-18 Antimony Aminophosphines, optically active ligands, biomethylation, 20340 18160-161, 167, 176, 180-181, 187, diheteroferrocenes and derivatives, 192-194 39325-351 Aminoplumbation reactions, 7:294-296 distibine, 30:77-97 2-Amino pyrrholes, synthesis, 4k203-204 heterocarborane, 30:141 Aminosilanes, 9276, 39187 organometallic chemistry, 14187-204 Aminosilyl anions, 3842 ?I complexes, 26:282-284 Aminosilylene, 39161 arene complexes, 26284 (Aminosilyl)lithium, 38:18, 42 carbollyl complexes, 26:282 (Aminosilyl)magnesium, 3819 cyclopentadienyl complexes, 26282 Ammine complexes structures, 26283 chromium, 3197-199,208,210 reaction with alkyl halides, 3872 Antimony 24

terphenyl derivativcs, &47 cobalt, rhodium, and iridium tetramethyldistibine anionic species, 3k1.50-151 diarsine comparison, 3093 bridging carbonyl, 3k149 dipole moment, 3091 cationic species, 31:151 electron diffraction, 3092 paramagnetism, 31:151 properties, 3078 phosphine derivative, 3k148 Raman spectra, 3091 steric consideration, 3k149 reactions, 3080-81 tnmetal species, 31:148 tctraphenyldistibine iron, ruthenium, and osmium cluster properties, 30:77 hydride, 31:139-140 Raman spectra, 3091 pentametal species, 31:141 structure, 3086-87 tetrahedral, 31:139 ylidcs, 14231-232 tetramctal species, 3k140 aryl derivatives, 14231 manganese and rhenium, 3k137 Antimony and bismuth transition metal tetraelement co m p I ex cobalt, 31:153-154 dielement cubic cluster, 31:153 bonding trimetal species, 31:135 Antimony heteroles, 39:327 bond length, 3k136 Antimony trichloridc, arene adducts, chromium, molybdenum, and tungsten, 26:284 3k135-137 cobalt, rhodium, and indium anionic Antimony(V) alkyls, 14232-236 specics Anti-stokes lines, 1:242 paramagnetic, 3k151 Apicophilicity, of silicon substituents, structure, 3k152 20272-275 synthesis mechanism, 31:153 Appearance potentials four-electron donor, 3k136 heats of formation of ions, iron, ruthenium, and osmium cluster 6316-323 anionic species, 31:145-146 of hydrocarbonmetal ions, 8:283-284. mutually bonded element, 315-319 3k141-143 aruchno-Carboranes mutually nonhonded element, brachiation intermediates and cations, 3k143-147 3615-16 synthesis, 31:143-144 compounds, 3640-47 synthetic interaction, 3k146-147 2-vertex. 36:46-47 thermodynamic control of isomer, 3-vertex, 3646 31: 144 4-vertex, 3645 trigonal bipyramidal geometry, 5-vertex, 3645 3k143 6-vertex, 3645 Zintl metal carbonylate, 31:145 7-vertex, 3645 manganese and rhenium, 3k137-139 8-vertex, 36:45 stabilization, 31:135 Y-vertex, 3645 monoelement 10-vertex, 36:42-43 bond length, 3k131-133 11-vertex, 3642-43 chromium, molybdenum, and tungsten 12-vertex, 3642-43 anionic, 31:130-133 electron counting, 36:31 mixed metal, 3k134 geometrical systematics and electron pair trigonal planar coordination, relationships, 3622-25, 27-28 3k133 Ziegkr-Nattd polymerization, 36:46 trimetal species, 3k134 Arbusov rearrangement, 26147 25 a-Arenemetal complexes

Arenecarboxylates, metal, thermal decar- access to boxylation, 25254-257 $cyclohexadienyl Os(I1) complexes, Arene-chromium chemistry, 37:292 29212-216 Arene-chromium complexes q6-cyclohexadienyl Ru(I1) complexes, chemical reactivity 29:212-216 electrophilic attack, 34293 diene Ru(0) complexes, 29217-219 nucleophilic attack, 34294 nucleophilic substitution, 29219-220 crystal structures, 34.285-287 oxidation, 29220-221 kinetic rotation, 34289-293 Arenemetal complexes, 3150, 153-154 NMR measurements, 34:287-289 a- Arenemetal complexes, 1347-137 solid state, 34319 bisarene complexes relaxation time studies, 34319 chromium, 1351-53,61-65 sterically crowded cyclopentadienyl com- cobalt, 1354,65-66, 111-112 plexes, 34319-321 EPR studies, 1354 theoretical calculations, 34:295-297 iridium, 13:115 thermodynamically restricted rotation, iron, 1354, 65, 93-94 34289-293 magnetic properties, 1353-54 tripodal orientation manganese, 1365,90-91 electrophilic attack, 34293 mass spectra, 1354-55 nucleophilic attack, 34294 molecular orbital theory, 1351-55 tripodal rotation neutron diffraction studies, 1351 electronic harriers to nickel, 1366, 117 benzyl chromium tricarbonyl cations, osmium, 1366,93 34312-316 photoelectron spectra, 1351-53 fulvene complexes, 34316-319 preparation, 1348-50 localized double bonds, 34:311-312 rhenium, 1391 steric harriers to rhodium, 1366, 111 (HEB)Cr(C)L’L” complexes, ruthenium, 1354, 65-66, 93-94 34306-310 stabilization by methyl substitution, (HEB)Cr(C0)2L complexes, 1393 34299-303 structure and bonding, 1351-55 (hexaethylbenzene) Cr(CO)?, technetium, 1365, 91 34297-299 titanium, 1357-58, 64 (pentaethylacetophenone)Cr(CO)?, tungsten, 1363, 65 34:303-306 vanadium, 1353, 58-60,64 sterically hindered arenes, X-ray diffraction studies, 1351 34:310-311 carbonyl complexes Arene complexes, structures, 598-100 chromium, 1355-56,70-89 Arene-containing clusters, of Ru or Os, cobalt, 13:79, 114-115 29234-235 iron, 1378-79,100-102 Arene cyclooctadienyl, 29190 manganese, 1378,92-93 Arene cyclopentadienyl osmium complexes, molybdenum, 1355, 70, 77.79 29201 rhenium, 13193 Arene cyclopentadienyl ruthenium com- ruthenium, 1379, 102 plexes, 29187 tungsten, 1355, 77-78 Arenedicarboxylates, metal, thermal decar- vanadium, 1359-60,71 boxylation, 25258-263 as catalysts, 1350, 58 Arene 2,4-dimethylpentadienyl ruthe- of copper, 13109,120-122 niurn(I1) complexes, 29:190 a-cyclopentadienyl complexes Arene ligand reactivity cobalt, 1397,112-113 a-Arenernetal complexes 26

iron, 1395-100 alkyl arene 0s intermediates, manganese, 1391-92 29198-200 molybdenum, 1369 arene 0salkyls. 29:195-196 rhenium, 1391-92 arene 0s allyls, 29195-196 rhodium, 13112-113 arene 0s carboxylates, 29195 ruthenium, 1395-97 carborane clusters, 29:201-202 tungsten, 13:69 hydrido arene 0s intermediates, dienerhodium complexes, 13108, 29198-200 115-117 hydrido-bridged complexes, 29196-198 halocomplexes osmaborane clusters, 29201-202 niobium, 1360-61, 105 phosphonate arene Os(I1) complexes, osmium, 13103,107-111 29200 ruthenium, 13:103- 104, 107-11 1 terminal arene Os(I1) complexes, tantalum, 1360-61, 105 29196-198 titanium, 1357-58, 105 vinyl Os(I1) complexes, 29200-201 zirconium, 1358, 105 [OsX2(arene)lz and [OsXl(L)arene] deriv- mass spectra, 8:216, 227-231, 239 atives, arene Os(L)(L')X+, in nitrogcn fixation, 1351 29:194-195 of palladium, 13109, 118, 120, 369 a-Arene-a-cyclopentadienylironcomplexes, of platinum, 13:109, 119-120 1044-47,407 reactions, 1350-51 NMR spectra, 1085-86 a arene displacement, 1350, 93, 99-100 Arene complexes nucleophilic addition, 1350, 98-99 gallium, 26:245-248, 287 structures, &245 of silver, 13109, 122-125 synthesis, 26247-248 Arenemetal tricarbonyls, 3211 Group VB metals, 26:284 Arene osmium alkyl complexes, 29195-196 Group V1 and VII elements, &286 Arene osmium ally1 complexes, 29:195-196 indium, 26287 Arene osmium carboxylates, 29d9.5 lead, a281 Arene osmium complexes manganese isocyanide, 11:56 as catalyst precursors, 29239-241 mass spectra, 6290, 301 Os(II) derivatives, hydrido-bridged, from substitution, 10365-370 29196-198 thallium, 26:257, 287 Os(L)(L')X+, 29194-195 tin, 26278-279 synthesis, metal vapors in, 29235-238 r)-Arene rings, Group 4B carbonyl com- terminal, from Os(I1) derivatives, plexes containing, 25375-376 29196-198 q6-Arene ruthenium, 29:163 Arene osmium(0) complexes, 29210-211 Arene ruthenium carbene derivatives, q6-Arene osmium(I1) complexes 29183 from OSCI~~-,OsO,, and OsC13(H20)3, Arene ruthenium complexes 29191-192 as catalyst precursors, 29239-241 from [OsClz(arene)] r) formation of mixed-metal derivatives, by arene ligand exchange, 29192 29~229-231 formation of (arene)OsX30s(arene)+, as precursors of Rulmetal derivatives, 29192-1 94 29229-233 by ligand substitution or addition, stereochemical aspects, 29:184-185 29:192 synthesis, metal vapors in, 29235-238 [OsXz(arene)12and [OsXz(L)arene]deriv- Arene ruthenium(0) complexes, 29202 atives, 29194-202 reduction of Ru(arene)?+, 2%207-208 acetylide Os(I1) complexes, 29:200-201 Ruo(arene)(L)z,formation of, 29208-210 27 Arsenic

from [RuCl2(arene)lzcomplexes, Arenesulfonyl halides 29204-207 desulfination by iridium complex, 1268 from Ru( $-cyclooctadiene)( g'-cycloocta- ruthenium complex, a65 triene), 29202-204 reactions with organocopper compounds, $-Arene ruthenium(I1) complexes 12.285 arene cyclopentadienyl Ru(I1) complexes Arene-titanium complexes, 9171-172, 183 introduction of arene and cyclopenta- Aromatic heterocyclic nitrogen compounds, dienyl ligand, 29:189-190 conjugate addition, 1:223 introduction of arene ligand, Aromatic hydrocarbons 29186-187 interaction with GIC, a98 introduction of cyclopentadienyl li- reactions with B2Cl4, 10260 gand, 29185-186 Aroxymethyl silanes, charge transfer com- transformation of ligand to arene li- plexes gand, 29187-189 absorption spectra, 34179, 183 transformation of ligand to cyclopenta- conformational effects, 34:182-183 dienyl ligand, 29189 donor properties, 34:178-179 from RuCL3, 29164-165 interaction, integrals of, 34182 from [RuC12(arene)12 ionization potentials, 34:179 by addition of ligands to [RuC12(ar- Arrhenius function, o-(al1yloxy)phenyl radi- ene)12, 29:165-167 cal, a77 by arene ligand exchange, 29165 Arsaalkenes, 39226 formation of (arene)Ru(m- Arsabenzenes, 39325 X)3Ru(arene)+cations, 29169-171 from arsacyclopentadienes, 13175 of Ru(arene')(arene')*+ complexes, reaction with alkynes, 13176 29: 167- 169 n-Arsacarbollide (BgH9CHAs2-)complexes, ruthenium borane complexes, 29~90-191 8:103-104 ruthenium carborane complexes, Arsacymantrene, 39333 29190-191 Arsanediyl, 39222 (RuX2(arene)l2 and RuX2(L)(arene) de- Arsanylketene complex, reactivity of, B44 rivatives Arsanylorganyldiazenes, 23:168-169 arene Ru alkyls, 29:172-175 Arsasilenes, 39194 arene Ru carbenes, 29183 molecular structure, 39195-197, 221-222 arene Ru carboxylates, 29171-172 properties, cyclovoltammetry, 39206 arene Ru complex stereochemistry, reactions 29184-185 cycloaddition, 39223, 225 hydrido(arene)Ru complexes, oxidation with white phosphorus, 29176-183 39:223 Arene ruthenium vinylidene complexes, thermolysis, 39222-223 29183 spectroscopy, 39221 Arenes synthesis, 39220-221 as bridging ligands in dipalladium com- Arsenic plexes, 19155, 178-179 anionic hydride complexes, spectroscopic cocondensation with Ru or 0s vapors, properties, 275, 8 29:163 biomethylation, 20346-347 hydrogen-deuterium exchange, 38167 by C. humicola, 20326-327 loss of aromaticity on bonding to mechanism, 20338-340 Fe(CO)I, 13:100-101 and speciation, 20341-342 reactions with metal atoms, 1S72-76 dicarborane, 30144-145 Arenesulfinic acids, reaction with palladi- diheteroferrocenes and derivatives, um(I1) complexes, U:69 39325-351 Arsenic 28

hetcrocarhorane, 30140-1 47 manganese, 3:214, 217, 221 preparation, 30141, 145-147 molybdenum, 3204 transition metal complex, 30144 nickel, 3248 heterocyclic compounds, see Heterocyclic osmium, 3:236 compounds, arsenic platinum, 3251 mixed-mctal complcxes with germanium, rhenium, 3:223 26267 rhodium, 3243 organic derivatives, see Arsine deriva- ruthenium, 3:236 tives; Organoarsenic compounds tungsten, 3204 terphenyl derivatives. M45-47 vanadium, 3195 Arsenic-arsenic bonds, 4:187-189 Arsine cyanides, 4:171 Arsenic-carbon bonds Arsine derivatives cleavage alkali metal, 4183-184 acids, 4176-177 boron, 4:184-185 bases, 4:177-178 Group IV elements, 4185 halogens, 4174-176 Group V elements, 4185-189 mcrcury compounds, 4178 halogens, 4195-198 thermal, 4:173-174 mercury, 4184 formation, 4146-173 nitrogen, 4185-186 Arsenic, ?r complexes, 26282-284 prcparation, 4147 carbollyl complexes, 26:282-284 4199 cyclopentadienyl complexes, 26:282 transition metals, 4:184 structure, 26:283 zinc, %285 Arscnic rooms. 1324-26 Arsine imines, Arsenic-silicon multiple bonds, 39:193-195 Arsinc oxides, 4189-193 arsasilenes, 39:194,220-227 Arsines, 29:165, see also Organoarsenic com- theory, 39195-197 pounds Arsenic transition metal clusters, catalytic preparation, 4182-183 reactions involving CO and H2*3581 by high energy particle irradiation, Arsenic(V) pentamethyl. 14:229-231 4172 Arsenic ylides, 14224-228 Arsine , 4195 NMR spectra, 14226-227 Arsine sufides, 4193-1 95 photoelectron spectra, 14228 Arsoles, 4152 reactions, 14:225 synthesis, 39:327-328 stability, silylation cffect, 14228-229 Arsonic acids structure, 14226 preparation, 4148-149, 156 synthesis. 14224-225 reactions, 4176 thermal stability, 14226 Arsonium compounds Arsenic ylids, 9292 synthesis, 4159, 168-169 Arsenide derivatives. multiple bonding, thermal decomposition, 4173-174 39:26-38 Arsonium ylides Arsenobenzenc (C6HSAs),, structure, 4:210 acetylated compounds. 20118-119 Arsenomethanc (CHIAs).5,structure, 4209 from arsonium salts, 20116-118 Arsine horanes. k301 canonical forms, 20116, 126 Arsine complexes, .see dso Bridged arsinc comparison with phosphorus co m p 1exes basicity, 20129 chromium, 3204 bonding of ylidic carbon atom, 20127, cobalt, 3:237-238, 240-241 131 iridium, 3245-246 ionization, 20132 iron, 3224, 229-231, 234 IR spectra, 20130 29 Arylmercury compounds

reactivity, 20116, 134-135, 137, ultraviolet spectra, 20129-130 153-155 a$-unsaturated nitrile formation, 20138 in cyclopropane synthesis 144-145, 20:147 Arylation mechanism, 20145 with C6F5X, 28228-229 product configuration, 20:143 of compounds MClz(tht)2, 28223-224 in heterocycle synthesis, 20150-152 of compounds [Pd(m-X)XLI2, 28223 via aminoketones, 20150 with (C62X&Hgr 28226-227 via anilines, 20152 direct, of Pd or Pt complexes, using Grig- via diazonium salts, 20152 nard and organolithium reagents, of isoxazoles, 20151 28221-226 of pyrones, 20150-151 of Kz[MC14], 28224-225 IR spectrum, and enolate, 20130 of MClz halides, 2tk226-227 mass spectra, 20132-134 of MXZLZ, 28221-222 fragmentation mechanism, 20133 of (NBU~,~[M~(~-B~)~B~~,28226 NMR spectra, 20126-128 with [T1(p-Br)(C6F5)2]2,28226-227 structure at ylidic carbon atom, 20131 Aryl azides, reaction with iminosilanes, olefin and oxirane formation, 20146, 154 39176 photoelectron spectra, 20132 Arylborane heterocyclics, synthesis, preparation, 20116-125 2271-275 reactions with carbonyl compounds, Arylboranes, 39367-368 20:134- 140 Arylboron dihalide, reduction, M20 aromatic aldehydes, 20137-138, 140, Aryl complexes, electron-transfer reactions, 147-150 23~34-36 ketones, 20135-139 u-Aryl complexes, 1055-56 mechanism, 20137 Aryl compounds, of alkali metals, 27:192- olefin yields, 20135 194,219-220 product isomerization, 20135-136 Arylcopper compounds, with dimethylam- a&-unsaturated esters, 20141-143 ino-substituents, 12:235-237 a,P-unsaturated ketones, 20144-145, Arylcyclopropanes, from aryldiazomethane 147 and olefins, a94 reaction with tropylium salts, 20146 Aryldiazenido complexes, hydrogenation, structure, 20:126-127 17:387 from tertiaryarsine oxides, 20118-120 Aryldisilanes, 3974, 80, 108 and active methylene compounds, photolysis, 2532 20118-119 Aryl groups, rearrangement, 39253-254 and electron-deficient acetylenes, Aryl halides, reduction with organotin hy- 20119-120 dride, k70-80 and nitromethane, 20119 Aryl hydrides, 28330 from tertiary arsines, 20120-121 Aryl iodides, from organothallium com- and acetylenes, 20121 pounds, 1k1.58, 165 and diazonium salts, 20:120 Arylisocyanates, cocyclization dihalides, 20118 with butadiene, 12178 transition metal complexes, 20152-153 with isoprene, 17:178 via transylidation, 20121-125 Aryllanthanides, 9366 acylation, 20122 complex anions, 9366 fluoroacylation, 20123-124 Aryl ligands, bulkiness, M2-3 of fluoroolefins, 20124-125 Aryllithium complex, ketene reaction, 288 formylation, 20122 Aryllithium reaction, 25182 mechanism, 20124 with nickel carbonyl, 847 of phenylsulfine, 20122-123 Arylmercury compounds, in palladium(I1)- Arylmercury compounds 30

catalyzed olefin oxidations, 13404- ionization potentials, 34166 405 quantum chemical parameters, 34:157 Arylmetal compounds, conversion to p-ar- silaindanes, ionization potcntials, 34163 ene complexes, 7A96 LT-nconjugation, extent of, 34160 Aryl migrations u-n interaction diagram, M160 in organo-group 1 compounds, tetracyanoethylene with 16:167-210 arylpolysilanes, 341 67 in rearrangement of quaternary ammo- benzencs, 34:159, 164 nium salts, 16:180 , 34156-157, 159-160 Aryloxides, multiple bonding. 3939-44 phenylpolysilanes, 34162-164 Aryl-palladium bimetallic complexes, vinylsilanes, 34152 31297 visible spectra, charge transfer bands, Arylsilane radical anions, 15283 34162-170 cleavage reactions, 15283 Voigt-Reid equation, 34166 coupling reactions, 15283 Arylsilyl anions, 383-1 1, 50 Arylsilanes, charge transfer complexes Arylsilyl ethers, charge transfer complexes absorption spectra, 34155 of analysis, 34162 absorption spectra, 34180, 183 bcnzene derivatives, charge transfer band charge transfer bands, 34180 maxima, 34159 conformational effects, 34182-183 Bishop’s hyperconjugation model, intcraction, integrals of, 34:182 34156-157 ionization potentials, 34180-181 charge transfer bands. frequencies of, Arylthallium halides. stability, 1M64 34156 ArylLtitanium(II1) compounds, 9171-172 complexation constants(K). 34168 Aryne-transition-metal complex electron withdrawing properties, notation, 42148 34156-158 structure and spectroscopy, 42185-186 Es values, 34160 synthesis and reactivity extinction coefficients, 34168 benzdiynes, 42:175- 177 highest molecular orbital method, 1,3,5-benztriyne, 42178 34156-157, 160 early transition-metal complexes of highest occupied molecular orbital, benzynes. 42:153-160. 162-168 34157-159, 161,165-166, 168-169 general syntheses and mechanism, hyperconjugation model paratmeters, 42: 148-1 52 34157 late transition-metal complexes of ben- ionization potentials, 34156, 158, 160 zynes, 42168-170, 172-173 LUMO, 34158-159,164 naphthalynes, 42178-181 molecular orbital interaction diagram, tropyne, 42181-185 34161 Arythalliurn trifluoroacetatcs molecular orbital perturbation theory, photolysis, 1k171 34: 159-160 preparation, 1k163-169 Mulliken charge transfer theory, 34160 reactions, 1k171-173 naphthalene derivatives, charge transfer with hydrides, 1k173 band maxima, 34159 with nitrosyl chloride, 1k170 naphthylpolysilanes use in organic synthesis, 1k169-173 charge transfer maxima, 34161 aryl iodides, 1M58 ionization potential, 34161 nitriles, 1k171 phenylpentamethyldisilane phenols, 1k1.59 charge transfer band paramcters, thiophenols, 1k172 34165 AszFe,(CO)s, synthesis, 42108 31 Azobenzene

[As(Fp},]+Cl-,synthesis, 4281 NOP)(PPh3), third-order nonlinear op- Asymmetric catalysis, chiral sulfonated tics, 43:379 phosphines, 3817% 18I Auger ionization, 11:212 Asymmetric cyclization Auger spectroscopy, in studies of heteroge- of diallyl ether, 12135-136 neous catalysis, 12368 of 1,6-heptadiene, 17:135-136 Autoxidation, of cyclohexa-l,4-diene, Asymmetric hydrogenation, 12338-361 13:369 with chiral ligands, 12357-360 Azaallene group, 10163 amides, 12357 l-Aza-2-boranaphthalene,39356 amines, 12357-359 9-Aza-lO-boraphenanthrene, 39356 sulfoxides, 12360 1,2-Azaborine, 39356 by hydrosilation, 12337, 354-356 Azabutadiene complexes, 10156 by nickel complexes, 12357 1-Aza-l,3-butadiene complexes, synthesis, by platinum complexes, 12357 4k204-205 by rhodium complexes of chiral phos- 5-Aza-l-chroma-1,3,5-trienes,synthesis of phines, 12338-356 2H-pyrrholes, 4k205,207 catalyst nature, 12351-353 Azacyclopentadiene ligand, reaction with DIOP complexes, 17:340-345 ketenes, 289-10 ferrocenyl phosphines, 12348-349 1,2,5-Azadiborolene, 18:303, 314 ligands derived from sugars, metal complexes, 18:324-325 Azadisilirane, 39259 12350-351 Azaferrocenes, 39325 optical purity and catalyst structure, 5-Aza-l-metalla-1,3,5,7-octatetraenes,syn- 12342-347 thesis, 4k207-208 by ruthenium DIOP complexes, Azepinones, synthesis, 4k210 12356-357 Azide complexes, iron carbonyl, 8:128, 145 with as hydrogen sources, Azides, see also Pseudohalides 12382-383 properties, 9215-217 by supported catalysts, 12366-367 reactions Asymmetric hydrosilation, via chiral plati- cycloaddition with disilenes, 39259, num complexes, 17:427-428,434 261 Asymmetric synthesis, of chiral metal com- with germenes and digermenes, plexes, 18186-188 39294-295 ate complexes, of mixed alkali metal com- with germylene, M146 pounds, 22218-235 with iminosilanes, 39176 nonorganic, 22221-235 with metal carbonyls, 10121, 129-131, halides, 22228-231 175, 184 hydrides, 22224-226 with silenes, 39133 oxides, 22235 with tin doubly bonded compounds, pseudohalides, 22231-232 39316-3 17 trimethylsilyl compounds, 22221, 224 Azido complexes, 10129, 184 organoalkali compounds, 22218-221 Azido-di-t-butylchlorosilane, 39163 alkyls, 22218-219 Azidosilaneimine, 39183 aryls and alkynyls, 22219-220 Azidosilanes, photolysis, 39160 a delocalized anions, 22220-221 Azines, cocyclization with butadiene, 12143 Atom-atom interaction model, %133 Aziridene complex, 22:279 Atom transfer, 2152 Azoalkanes, thermolysis, 23143-144 Au(CE CC~H~-~-CECC,~H~-~’-NO~)(PP~,),Azobenzene third-order nonlinear optics, 43379 a-backbonding ability, 1457 Au(CECChH4-4-(E)-CH=CHCbH4-4’- complexes, 10132-133 Azobenzene 32

MO calculations on, 1457 physical properties, 40.295-296 Ni(0) complexes, 1457 synthesis, 40291 reactions with Ni, Pd, and Pt compounds, chemical vapor deposition 10403-404 alkoxides, 40250, 253, 263-265, 315 Azobisisobutyronitrile, as radical initiator, carboxylates, 40:324-325 14347, 380 cyclopentadicnyl compounds, 40311 Azoboranes, 23161 P-diketonates Azo compounds fluorinated compounds, 40315-316 as ligands, 23181 Lewis base adducts, 40.319-320 nitrogen-bridged iron carbonyl deriva- metal oxide film precursors, tivcs, 10134 40317-319 ortho-metallated, 10132 monodentate donors, 40320 reactions with metal carbonyls, polydentate donors, 40:320-324 10:131-134 thiocarboxylates, 40:326-327 complexes, 3107-113 diacetamide compounds iron, 4366, 368 physical propertics, 40:296-297 manganese, 4367 synthesis, 40:291-292 mass spectra, 8239, 272 P-diketonates molybdenum, 4366 crystal structures, 40:276-278, 280, 282 palladium, 4368 mass spectrometry, 40:282-283 rhodium, 4368 physical properties, 40265-271, 275, Azulenium chromium complexes, 4:367-368 281 polydcntate compounds crystal structures, 40.286, 289 B mass spectrometry, 40:289-290 Backbonding, in metal carbonyls, 2176-177 physical properties, 40:284-285 n-Backbonding, azobenzene, 1457 synthesis, 40:283-284 Bailar twist, 35271 synthesis, 40:273-275 B-alkenylboracyclanes. hydroboration, types, 40272 2275 volatility, 40:281, 283 B-alkylboracyclanes P-ketoiminates alkyl cxchange, 2258-259 physical properties, 40:265-271 stability of ring system, 2263-264 types, a272 synthesis: by displacement, 2280 metallocenes by hydroboration, 2:217 crystal structures, 40243-244, 246-249 thermal isomerization. 2262-264 gas-phase electron diffraction, 40246 Barbiturates, sedative activity and substitu- Lewis base removal, 40937-238 ent chain length, 18281 mass spectrometry, a246 Barium physical properties, 40:239-243 alkoxides stability, 40:236-237 crystal structures, 40.255, 261-263, 265 synthesis, &237-239 NMR, a263 monocyclopentadienyl compounds physical properties, 40:255-259 physical properties, 40:297-298 synthesis, 40:2S3-255 synthesis, 40:292-293 amides phosphides crystal structures, 40:230-231, 234-236 crystal structures, 40230-231, 234-236 physical properties, 40:226-227, 230, physical properties, 40226-227, 230, 232, 234 232, 234 synthesis, 40:224-225, 228-230 synthesis, 40:224-225, 228-230 carboxylates polydentate ligands 33 Benzheterocycles

crystal structures, 40:302, 304-305, 307, chlorination via Pt(I1) complexes, 309 15177-179 physical properties, 40:299-301 cocondensation with osmium, 29237 synthesis of compounds, 40298-299 inorganic, 39356 poly(pyrazoly1)borates Pt(I1)-catalyzed H-D exchange, physical properties, 40:250-251 15158-177 structures, 40:250 Benzenechromium tricarbonyl, mass spec- synthesis, 40:249-250 trum, 6290, 8227 selenolates derivatives, mass spectra, 6:306, 311 physical properties, 40:293-295 ring-substituted derivatives, 8227-231, synthesis, 40:290-291 289-290 sulfonates a-Benzenechromium tricarbonyl, neutron ir- physical properties, 40:295-296 radiation, 1k229 synthesis, 40:291 Benzene cyclopentadienyl ruthenium@) thiocarboxylates complex, 29216 physical properties, 40:295-296 Benzene-1,2-diolato(2-) bidentate ligand, synthesis, &291 in spirocyclic A"Si-silicates Barium-graphite intercalation compounds, ab initio studies, U232-233 2896-97 chemical properties, a235 Bart reaction, 4:156-158 geometry optimization, 44:232-233 Basicity NMR studies, 44:233-234 acylmetalloids, 2114 synthesis, M230 metal, effect on carbene complex reactiv- X-ray diffraction analysis, 44:230-233 ity, 25127-129 Benzene-metal complexes, 1:291-302 Basis function, mathematical descriptions, analysis of benzene spectra, k291-292 42:309 benzene-metal carbonyls, 1:299-301 Bechamp reaction, 4:148 dibenzene-metal complexes, 1:256, 293- Benchrotrene complexes, 8227-231, 299, 310 289-290 substituted benzene complexes, Benesi-Hildebrand method, M187 1:301-320 Bennett's procedure, 29221 Benzene-2-methylpropane, cocondensation Bent rehybridization theory, application to with osmium, 29238 methyltin halides, 14:71 Benzene osmium(I1) phosphonates, 29200 Benzalacetophenone, reaction with silenes, a-Benzenela-alkyl bi- and trimetallic com- 39125 plexes, 32292-300 Benzaldehyde a-Benzenela-carbene bi- and trimetallic coupling with Ti-gr, 28127 complexes, 32300-301 reactions with a-Benzene/a-carbyne bi- and trimetallic germenes, 39296-298 complexes, 32300-301 iminosilanes, 39175 Benzenesilanitrile, 39161 tin doubly bonded compounds, Benzenetricarbonyliron, 26323 39314-315 Benzheterocycles, 13176-195 Benzannulation, alkynes, a278 benzcyclobutene derivatives, of silicon, Benzdiynes, transition-metal complex syn- 13177 thesis and reactivity, 42175-177 preparation, 13179 Benzene benzcycloheptene derivatives, 13183, addition to diphenylketene, 2816 185, 188-189 anion radical, 16200 reactions, 13184 ESR spectrum, 16200 silicon, 13183-184 hydrolysis, 16:200 tin, 13183 Benzheterocycles 34

benzcyclohexene derivatives, 13179, Benzoylcyclopentadienylsodium, synthesis, 187- 188 43270 arsenic. 13181 Benzoyloxyl radical, reaction with Sn hy- boron, 13179-180 drides, 44:99, 101 silicon. 13180-182 Benztriyne, transition-metal complex synthe- henzcyclooctene derivatives, of silicon, sis and reactivity, 42178 13183-185, 189 Benzvalene. 314 benzcyclopentene derivatives, 13179, Benzylboranes, 39368-369 186-187 Benzyl bromide, reaction with metals, 38:73 aluminum, 13181 a-Benzyl complexes, conversion to n-allylic arsenic, 131 81 group, R195 boron. 13179-180 Bcnzyl compounds, of alkali metals, silicon, 13180-182 2R196-201 nomenclature, 13:177-178 Benzyl halides, reactions with nickel car- radical anions of Group IVB derivatives, bonyl, 8:47 15291,295-296 BenzyHithium-1,4- Benzhydryl ethers, silybdtcd, 18286-287 diaza[2.2.2]bicyclooctane, 26218-219 Benzil, reaction with disilenes, 39261-262 Benzyl mangancscpentacarbonyl, reactions, Benzilic acid, in spirocyclic A’%-silicates, 37:192- 193 U241 Benzylpotassium, synthesis and structure, 43271 Benzocyclobutane. 39:140 $” -SH-Benzocyclohcptenedicarhonyl- Benzyl radical, reaction with Sn hydrides, a94 trimethylphosphitechromium Benzylruhidium, synthesis and structurc, isomerism. 26325 43271 structure, 26:323-324 Benzyne, transition-metal complex synthe- synthesis, 26~323 sis and reactivity, 42153-160, 162-170, Benzodisilacyclobutane, chemical behavior, 172-173 39110-1 11 Benzyne ligand, migration in triosmium Benzohydroximato(2-) bidentate ligand, in cluster, 16:339-340 spirocyclic h5Si-silicates Berry pseudorotation, 35275 NMR studies, 44:255-256 in iron olefin carbonyl complex, synthesis, M255 16231-232 Bcnzonitrile, reactions in metal carbonyl substitution mecha- with arsasilenes. 39225 nism, 21:134 with phosphasilencs, 39219 Beryllium Benzophenonc acyclic pentadienyl complexes, coupling with Ti-gr, 28:127 26:130-131 reactions with rcaction with electrophiles, 26132 germenes, 39296-298 aryls, 9204 phosphasilenes, 39213-214 borane complexes, 2k63-65, 82 tin doubly bonded compounds, chelate complexes, 9213-217 39314-315 coordination compounds, 9207-213 Benzophenone-iminosilane adducts. 39169, dicyclopentadienyl, 9205 178, 181 heterocarborane, 30104-105 Bcnzophenone-silene cycloadducts, preparation, 30104 397 23- 124 structure, 30105 Benzosilacyclobutene, 39:250 methyllithium derivatives, 24394 Benzosilole anions, 3825 mixed alkali metal compounds, Bcnzostannepins, 13 192 2T226-227 35 Bimetallic complexes

a complexes, 26226-231 [Bi4C09(C0)16]2-,structure and bonding fac- alkyne complexes, 26:226 tors, 42:33 cyclopentadienyl complexes, [BixCo14(CO)zo]2-,structure and bonding 26226-231 factors, 42:33 dicarbollyl complexes, 26231 BiCo3(CO)s, synthesis, 4297 reactions with B~[CO(CO)~PP~~]~,synthesis, 42116 acyl halides, 9:222 BiZCo2(C0)4(PPh3)2,synthesis, 4277 alkyl halides, 9219 Bicyclobutanes, 39267 dialkylmercury, 9200 Bicycloheptadiene, substituted complexes, Beryllium alkyls, 9196-204, 219 k18-19,28 amino derivatives, 9222-230 Bicyclo[2.2.0] hexastannanes, 38:233-235, chemical properties, 9203 237-238 complexes, 9221 Bicyclo[4.2.0]octa-2,4-dieneironcomplexes, 0x0 derivatives, 9:230 4381 potassium fluoride complexes, 9202, 239 Bicyclo[S.l.O]octa-2,4-dieneironcomplexes, preparation, 9200 4382 reactions with alcohols, 9232 Bicyclo-a-allylic metal complex, 2:348 ammonia and amines, 9:226 Bicyclo[l.l.l] pentastannanes, 38234, 236, redistribution equilibria, 6203 238-239 structures, 9197 Bidentate ligands thermal stability, 9204 acetohydroximato(2-), 44.255-256 benzene-l,2-diolato(2-), M230, 232-235 thio derivatives, 9:236 benzohydroximato(2-), 44:255-256 Beryllium borohydride, 9250 ethane-1,2-diolato(2-), 44:239-240 organo derivatives, 9251 ethene-1,2-diolato(2-), 44:236-239 Beryllium, bridged electron-deficient com- naphthalene-2,3-diolato(2-), 44:230-235 pounds, 15251-255 salicyIato(2-), 44:252-254 aluminum derivatives, 15263 Bidentate phosphorus ligand, replacement lithium derivatives, 15265-266 with 2-butyne donor, 2910 structures, 15251-254 [BilFe(Co)4t413 theoretical studies, 15255 structure and bonding factors, 428-9 Beryllium compounds, terphenyl deriva- synthesis, 4296 tives, 44:lO-12 [BiFe3(CO),"I-, synthesis, 4295 Beryllium halides, alkylation, 9201 [Bi4Fe4(CO)13]2-,synthesis, 4288 Beryllium hydride derivatives, 9241 Biferrocenes, 32135 Beryllium organo derivatives, 9195-253 Biferrocenylene, 3213.5 chelate complexes, 9213-217 BiIr3(CO)s, synthesis, 4277 amines, 9214 Bimetallic complexes bipyridyl, 9216 u-alkyl complexes oxygen compounds, 9215 a-alkenes, 32224-235 complexes with monodentate bases, a-alkynes, 37:246-265 9207-213 a-allyls, 32235-246 Group V elements, 9208-211 allenylidene complexes, 37:62-64 Group VI elements, 9211-213 a-benzene complexes Beryllocene, see Dicyclopentadienyl- u-alkyls, 32292-300 beryllium u-carbenes, 32300-301 Bibenzyl, 39370 a-carbynes, 32300-301 Bibismole, conformation, 39:340 u-carbene complexes Bi[Co(CO)&, synthesis, 42102 a-alkenes, 32266-270 [Bi{Co(CO),t4]-,synthesis, 42118-119 a-alkynes, 37:272-275 Bimetallic complexes 36

a-allyls, 37:270-272 Biphenyl alkali metal radical anions, struc- with carbon-heteroatom p bonds, tural data, 22245 32301 -304 Biphenylene, 496 a-cyclopentadienyl complexes p-Biphenyly(m-carboxyphenyl)phenylarsine, o-alkyls, 32275-288 resolution, 4214 o-carbenes, 32288-290 2,2’-Bipyridyl complexes u-carbynes, 32290-291 aminoberyllium alkyls, 9:229 n-a-bridging ligands in, 32219-310 beryllium alkyls, 9216 with pseudoaromatic heterocyclic p-li- titanium, 9181 gands, 32304-308 Bisacetato ruthenium complex, 29178 Bimolecular coupling, vinylsilanes, via radi- Bis(acet0)ruthenium arene complexes, cal anions, 15278 29171 Bimolecular homolytic substitution reac- Bis(accty1cne) metal complexes, synthesis tions, with free radicals, 14370-381 of, 28:244 main group compound substrates, Bis(acety1ide) rnctal complexes, third-order 14371 -373 nonlinear optics, 43379-385 transition metal complex substrates, Bis(acro1cin)-nickel, reaction with alkynes, 233 14373-381 Bis(acrylonitri1e)-nickel Bimolecular reactions, silenes, 39133-138 adducts with triphenylphosphine, 214- 15 addition of alkoxysilanes, 39136-137 catalytic reactions other additions to S-C double bond, with norbornadiene, 2:37-38 39137-138 with olefins, 237-38 reactions with MO description, 214-15 alcohols, 39133-136 reactions oxygen, 39138 with alkynes, 232-35 23319 Binary carbonyl complexes, with nickel carbonyl, 213-15 Binuclear carbene complexes, synthesis, structural analogs, 215 4k222-223 Bis-alkenylallenylidene complex, 3252 Binuclear cumulenes, synthesis, 4k230 Bisalkylidyne clusters, 3267 Binuclear metal carbonyl compounds, syn- Bis(alkyl)ruthenium(II) complex, 29173 thesis, 2W106 Bisalkynebisdithiocarbamate complexes, Binuclcar transition metal hydrides 2911 hydride ligand bonding, 2216 Bisalkyne complexes spectroscopic properties, 226-7, 23 six-coordinate, 2916 structural characteristics, 2216-17 structures, 2932-34 Bioamplification, metals, m.332 synthesis, 2913-18 Biogeochemical cycling, via transmethyla- Bis(allyl)nickel, 26:141, 143 tion, 20330, 343-345 Bis(a-allyl)nickel, in synthesis of 1,5-hexa- Biological methylation, 1324-25, 3871 diene, 833 of mercury, 1327 Bis(n-a1lyl)nickel complexes, 241-43 Biological organometallics, 1333-34 properties, 2:42-43 Biological process, transition metals in, Bis( arene)chromium complexes, see Arene- 2203 chromium complexes Biological systcms, organometallics in, Bis(arene) complexes, 32162 10339 Bis(arene)iron(II) dications Biomethylation, 20313-356, see also Trans- as electron acceptors, 33106-117 methylation ferrocene, charge-transfer complexes with Bi20s7(CO)y,structure and bonding factors, spectral characterization, 33107 42:20-2 1 X-ray crystallography, 33107-109 37 Bis(ethy1ene)rhodium

ferrocenc and arene donors, charge-trans- reactions with butadiene and carbonyl fer structures of, 33111-117 compounds, 839 back electron transfer, 33116 synthesis of long-chain conjugated poly- orbital correlation, 33:112 enes, 8:37 photoactivation, 33113-114 Bis(cycloocta-1,5-diene)nickel, 238-39 photoefficiency, variation of, 33115 d4 Biscyclopentadienyl alkyene complexes, ferrocene and aromatic donors, com- seven-coordinate, 29:13 plexes with Bis(cyclopentadieny1)metal complexes, oxi- charge-transfer, 33109-111 dative addition reactions, 26183 photoinduced electron transfer, Bis(cyclopentadienyl)(o-fluorobenzyne) 33109-1 11 titanium, 32297-298 spectra, 33:llO Bis(cyclopentadienyl)titanium, 9175-179 Bisarene transition metal complexes Bis(cyclopentadienyl)titanium(III) com- radical anions, 15312-313 pounds, 9162-170 radical cations, 15312 aqueous chemistry, 9163-166 Bisaryloxidzs, 3939 nonaqueous studies, 9167-170 Bis(azu1ene) iron, 4368 alkoxides, 9169-170 Bisbenzene osmium complex, 29235 organo derivatives, 9168 Bis[bis(trimethylsilyl)amino]germylene, Bis(cyclopentasilany1) mercury, 3833 39289 Bis(cyclophane)ruthenium(II) complex, Bis(bis( trirnethylsilyl)methyl)di(rnethyl- 29:221-222 thio)stannane, 39318 Bisdiazoalkane, photolysis, 39109-110 Bis[bis(trimethylsilyl)methyl]germylenes, Bis(dichlorobory1) alkanes, 2:317 39289-290 1,2-Bis(dichloroboryl)ethane Bis[bis( trimethylsilyl)methyl] tin, 38194 alkylation, 10266 Bis(boracyc1anes) alkyl exchange properties, 1&265-266 aminolysis, 2310 Bis(diethylboryl)acetylene, 39366 B-alkylboracyclanes, 2258 1,2-Bis(2,6-diisopropylphenyl)-l,1,2,2- dimerization energy, 2310 tetrachlorodisilane, 3223-24 by hydroboration, 2:275 Bis(dimethy1arsenic) disulfide, structure, stability, 2305 4204 Bis(boracycly1) alkanes Bis(dimethylphosphine)ethane, as blocking synthesis by hydroboration, 2:275 agent, 26:141 thermal isomerization, 2265 Bis(dimethylposphino)rnethane, 32242 Bis(boralanes), 2317 Bis(diphenylarsenic)oxide, structure, 4202 dissociation-association equilibrium, 2:307 Bis(diphenylphosphino)ethane, 37:252 IR spectrum, 2311-312, 314 Bis(diphenylphosphino)methane, 32242, preparation, 2305-307 255 reactions, 2:308-312 1,3-Bis(diphenylphosphino)propane,manga- Bis(borinanes), 2314 nesepentacarbonyl alkyl reaction, Bis(tert-butydimethy1silyl)hydrazine 32195 crystal structure, 4012, 14 [1,3-Bis(diphenylphosphino)propane]- synthesis, 40:12 (methy1hydroxycarbene)tricarbonyl- Bis(l-tert-butyl-2,3-dimethyl-1,2- manganese(I)triflate, 37:195 azaborolinyl)tin, 26:277-278 trans-Bisdiynyl ruthenium monomer, 3252 Bis-(t-butyldimethylsilylamino) Bis(duroquinone)nickel, electronic struc- fluorophenylsilane, 39188 ture, 223-24 Biscyclohexadienyl osmium(I1) complex, Biselenide, see Chalcogens 29236 Bis(ethylene)rhodium, as catalyst in ethyl- Bis(cyclooctadiene)nickel, 837-39, 26154 ene dimerization, 26198 Bis(ferroceny1)telluroketone 38

Bis(ferrocenyl)telluroketone, isolation, alkyls, bond dissociation energies, 2105 43126 aryls, reversible insertion of sulfur diox- Bis(germanimines). 39290 ide, 1237, SO Bis(germyl)ketones, 2139-143 compounds preparation, 2139 /3-decay to polonium, 11:235 reactions, 2140, 142 dibismuthine, 3077-97 Bis( 7-cyclopentadienyl)dicarbonylhafnium, diheteroferrocenes and dcrivatives, formation of, 25336 39:325-351 Bis( 7-cyclopentadienyl)dicarbonyltitanium, germanium compound, 21:274 formatiodpreparation heteroles, 39327 via other titanium complexes, 25331-333 terphenyl derivatives, M47-50 by reductive carbonylation of Cp,TiC12/ Bismuth, pentaaryl compounds (CpzTiC1)2,25322-324 Berry pseudorotation, 34:209 via titanocene alkyl and aryl complexes, bond length systematics, 34211 25324-331 charge-transfer absorption, 34:212 Bis( 7-cyclopcntadien yl) color, -212-216 dicarbonylzirconium, formation of, crystal structures, 34:209-211, 214-21 5 25333-336 hypsochromic shift, 3421 3 Bis( hexafluoroacetylacetonato)palladium, molecular orbital diagram, 34:215 37:244 NMR measurements, -212 Bishop’s hyperconjugation model, preparation, 34208 34156- 157 properties, 34:209-210 Bis( 7-pentamethylcyclopentadienyl) square bipyramidal structures, 34208- dicarbonylhafnium, formation of, 209, 212-215 25341-342 structures, 34208-212 Bis( 7-pentamethylcyclopentadienyl) substitution ii~.structure, 34:212-213 dicarbonyltitanium, formation of, symmetry, 34216 25336-338 trigonal bipyramidal structures, 34208- Bis( 7-pentamethylcyclopentadicnyl) 209,212-215 dicarbonylzirconium, formation of, uv spectra, 34:213 25338-341 Wittig method, 34:208 Bis(iron-aryl) complexes, 32298 Bis(a-allyl)nickcl, 614 Bis(ketene) complex Bis(pentadienyl)dinickel, 26:135 formation of, 2831 Bis(pentadienyl)iron, 26136, 141 structural data, 2841-43 Bis(pentadieny1)metal complexes, Bismabenzene, 39325 26135-140 Bismaferroccne, 39:333 Bis(pentaniethylcyclopentadieny1)arsenium Bis(mcthylcyclopentadienyl)tin,26268-272 tetrafluoroborates, 26282-283 bond angles, 2fk270 Bis(pentamethylcyclopentadieny1)stibenium bond lengths, 26:270 tetrafluoroborates, 26:282-283 structure, 26271 1,4-Bis(pentamethyldisilyl)benzene. photoly- synthesis, 26268-269 sis, 39108-109 Bis(methylene)propenylphosphorane, syn- Bis(phosphino)carbene, deprotonation, thesis with phosphaalkenes, 4k19 M182-183 Bis(methyl)ruthenium( 11) complexes, Bisquinuclidine, tluorenyllithium complex, 291 74-1 75 26219-220 I ,4-Bis(1-methyl-1 -silacyclobutyl)benzene, Bis-silene, synthesis, 3975, 110 pyrolysis, 3975 Bis-silyderivatives, Group 12 metals, 383 Bismoles, 39:330, 333 Bis(silyl)aminoorganyliminosilanes, 39182 Bismuth Bis-silyletene, 39:147 39 Bond cleavage

Bis(silyl)ketones, 2139-143 dimethylsulfate, 23162 preparation, 1139 diorganylboron halides, 23161-162 reactions, 2140, 142 germanium tetrachloride, 23165 1,2-Bis(supersilyl)disilane, 37:34 halogens, 23160 Bisthiolates, 39:46 hexachloroethane, 23164 Bis(triethy1phosphine)nickel-benzyne com- metal halides, 23172-173 plex, synthesis, 42152 monochlorosulfanes, 23169-171 Bis(trifluoroaceto)ruthenium arene com- monohaloamines, 23:166 plexes, 29:171 monohalophosphanes, 23166-169 Bis( 1-trihydrosila-3-butyl)benzene, dehydro- nitric oxide, 23176 coupling for polymerization, 42382 nitroso compounds, 23176-177 1,2-Bis(2,4,6-triisopropylphenpyl)-1,1,2,2- organolithium compounds, 23179-181 tetra(f-butyl) distannane, 38199 oxygen, 23160 Bis( trimethylgermy1)diazene phosgene, 23163 preparation, 23:125 phosphazenes, 23177-178 thermolysis, 23145, 147 silicon tetrafluoride, 23164-165, 181 Bis(trimethylsilyl)butadiyne, double silyla- sulfur and , 23160 tion, 43210 sulfur halides, 23170-172 Bis(trimethylsilyl)diaryldisilenes, 39241 sulfur imides, 23178 Bis(trimethylsily1)diazene sulfur oxides, 23178-179 complexes, 23181 -189 tetrahalomethanes, 23163 with cuprous halides, 23182 tin tetrachloride, 23166 with cyclopentadienyl halides, trihalomethanes, 23163 23:185-189 trihalophosphanes, 23169 with metallocenes, 23182-185 N,N-Bis( trimethylsi1yl)hydrazine dimeric lithium salt, 23159 crystal structure, &10-11 electronic spectrum, 23143 isomerization, 4&6 electronic structure, 23139, 142 synthesis, #:6-7 hydrolysis, 23152-155 Bis(trimethylsilyl)magnesium, 3813 reaction rate, 23153 Bis( trimethylsilyl)methyltrichlorogermane, as Lewis base, 23156 3R29 preparation, 23134 N,N’-Bis(trimethylsilyl)silanediimine, 39183 radical reactions, 23157 1,4-Bis(trimethylstannyl)-1,3-butadiene, reduction to anions, 23156-159 39330 similarity to diazene, 23:144 Bis( tripheny1phosphine)carbonylrhodium structure, 23139 hydride, as catalyst in ethylene hydro- thermolysis, 23144-149 formylation, 26:199-201 dimerization, 23144 Bis(triphenylphosphine)platinum(O), cyclo- disproportionation, 23144 pentyne complex, 42187 mechanism, 23146-149 Bisulfide, see Chalcogens silyl radical intermediates, 23146-147 Bloch-Siegert shifts, 28:402-404 Bis(trimethylsilyl)diazene, reactions Bond breaking, radiochemical studies, alkali metals, 23157-159 1k217 azides, 23:179 Bond cleavage carbon dioxide, 23:174-175 arsenic-carbon, 4173-182 , 23:174-175 boron-carbon, 4314-321 carbonyl compounds, 23175-176 boron-hydrogen, 4:310-314 , 23174-175 carbon-cobalt, 4:253-257 dihalomethanes, 23162-163 carbon-germanium, 4327 dihalophosphanes, 23169 carbon-mercury, 4304-307, 329 Bond cleavage 40

carbon-silicon, 4327-330 Bondi data set, 36:126-127 carbon-tin, 4327-330 Bonding germanium-gcrrnanium, 445-47 acylmetalloids, p,-d,, 7A31-139 in a-hetcrodiazoalkanes, 9414 alkynyl bond. 3880 hydrogen-silicon, 4:330-332 carbon-carbon triplc bond, 3880, 100- hydrogen-tin, 4332 105, 121-138, 172 lead-lead. 473-77 carbon-halogen bond scission, 3860, Si-Si bond 63-64 by bases, k106 carbon-metal bond, 38:lOS-116. 136-137 by halogens, 1:107 carbon-ruthenium bond, 3888-89, 104, mcchanism, 1:107-110 114 by organometallic reagents, 1:106 carbonyl groups to metals, 10208-211 silicon-silicon. 491-35 carboranes, 3307-308 tin-tin, 453, 58 comparison of CO and RNC, 1k25 Bond dissociation encrgies. 8284-286 C-R bond, 38116-117, 136-137 dcfinition, 25-51 dicarbollyl complexes of copper and Group 14 hydrides, 4468-70 gold, 8100 hydrocarbon-metal complexes, 8319-320 electron deficient beryllium compounds, mean 9197. 251, 253 mercury alkyls, 2100-105 in electron-deficient main group com- metal-carbon bond, 298- 100 pounds, 15236-230 metal carbon bond by carrier gas with hydride bridgcs, 15236 flow, 2:105 gold-phosphorus bond, 38:119 tables of, 2100-106 n-Bonded hydrocarbon ligands Group IV-carbon bonds, 2244 acyclic, Group 4B carbonyl complexes isocyanide complexes, 1k23 containing, 25372-374 lanthanide cyclopentadienyls, 9371 carbonyl complexes not containing, ligands, 3186 25319-322 metal carbonyl cations, 8118 rr-Bonded organometals metal carbonyls, 3:185 alkyls, 136-10 in metal complexes with arenes, 598-100 cacodyl, 134 with conjugated dioletins. 5100-105 diethyl zinc, 135 with cyclic conjugated ligdnds, in organic synthesis, 1310-12 5Y4-100 of transition metals, 1329 with a-cyclopentadienyl groups, Bond energies 594-98 absolute, definition, 2108 metal nitrosyls, 7:212 germanium-germanium, 4:45 in metal r-complexes of boron heterocy- intrinsic metal-carbon, 2:108-110 cles, 18304-307 Mulliken’s formula, 2:108-109 electron-counting methods, 18304-306 metal carbonyls, 210 multiple, see Multiple bonding silicon-silicon, 429-30 orbital energy diagrams, 2132-133 tin-tin, 458 organolithium compounds, 3371-380 Bond encrgy modcls in organolithium Compounds, 15260-262 Allan. 253 organosilicon compounds, dp-dp, 235 Fajans, 252-53 platinum-chloride bond, 38:117-119 Laidler, 253 in pseudohalides, 5181-193 Bond encrgy term values, 250-52 samarium indenyl, 9377-378 metal-carbon bond, 2:97-98 in silicon compounds, 545 Bond cnthalpics, of metal carbonyls, 2641 in silyl-substituted n-ligands, 15115 41 Borabenzene metal complexes

theoretical studies of organometallics, tetraethylethylenediamine adduct, 151-45 26:234 tin-tin bond, 38203-204, 209-210, 222- dicyclopentadienylarsenic, 26283 223, 235 dicyclopentadienyllead complexes, 26280 in transition metal carbynes, 2752-53 dicyclopentadienylmagnesium, 26:232 in transition metal complexes dicyclopentadienyltin complexes, 26270 cyclobutadiene, 4101-102 diheteroferrocenes, 39335 cyclooctatetraene, 4:375-376 2,4-dimethylpentadienylmetalcomplexes, valence tautomerism, 4357-360, 26:140 378-379 dodecacarbonyltriosmium, 2640 a-Bonding germanium doubly bonded compounds, boron-carbon multiple bonds, 39359-364 39277-280 boron compounds, 392 indium a complexes, 26:249 diheteroferrocenes, 39338-339 lead-lead, 471 disilenes, stable, 39239, 247-248, 255, metallocenes, 26140 266 mixed-metal triosmium clusters, 2674-75 gallium-iron, 3951-52 multiple bonding, 394-6 indium-iron dimers, 3955 pentadienyltricarbonylmolybdenum com- indium-molybdenum, 3955 plexes, 26152 Main Group 3-5 and 3-6 bonding, silenes, 3994-95 3914-17 silicon-silicon, 429-30 Main Group 3 compounds, 393-4 tin doubly bonded compounds, 39305 triosmium clusters, 265-6 to main-group elements, 26217-295 Bond order, germenes, M120 metal amides, 3923-24,26 Bond stability phosphorides, 3928-29, 33, 38 boron-carbon(aryl), 2274 phosphorus-carbon, 39193 thermodynamic silenes, 39100 perfluoroalkyl-lithium compounds, silicon-carbon, 2519 1:153 strengthening, 3962-63 perfluoroalkyl-tin compounds, k154 transition metal complexes, 3950 perfluoroalkyl-transition metals, k154 Bonding models of carbene complexes, Bond strength 25123-125 alkyl tin hydrides, k64 carbene fragment, 25123 aryl tin hydrides, 1:64 charge distributions, 25124 Borabenzene coordination to a metal, 25123-124 anions, 18: 303, 314-315 geometries of, 25124-125 as a ligands, 26256 substituent effects, 25124 bis complexes Bonding orbitals, see Molecular orbitals cobalt, 13112 Bond lengths iron, 13:176, 253 acyclic pentadienyl ligands, 26139 n-cyclopentadienyl cobalt complex, alkali metal organics, 27:185-190 13112, 174, 253 aluminum n complexes, 26242 Borabenzene metal complexes bromine-benzene adduct, 26285-286 acylation and ring-member substitution, cyclopentadienylgermanium complexes, 25230-232 26258-260 applications of, 25232 cyclopentadienyl ligands, 26139 bonding of, 25205-207 cyclopentadienyllithium complexes, compounds and synthesis methods, char- 26221 acterization, 25211-215 cyclopentadienylmagnesium bromide, electron transfer reactions, 25223-225 Borabenzene metal complexes 42

electrophilic addition reaction, 25230 Boracyclopropene, 39362 fission of metal-ligand bond Boradecalins, preparation, 2286-287 ligand substitution, 25227 Boraethenes, 39:370-372 ligand transfer reactions, 25226 9-Borafluorenes, synthesis, 2294-296 HID exchange, 29230 9-chloroborafluorenc, 2317 history of, 2520-202 dinierization tendency, 2310 ligand geometry, 25203 with organometallics, 2301 NMR spectra, 25207-209 Boraindanes, 2317 nomenclature, 25200 dimcrization tendcncy, 2310 nucleophilic addition reactions, B-halo, 2315-317 25227-228 preparation, 2288-294 nucleophilic substitution at boron, reaction with alkali metal, 2303-305 25228-230 with organometallics, 2:297, 300-301 structure, 25:202-205 spectra, 2304 synthetic methods Borane-carbonyl (BH?CO), 2290 alkali metal horatabenzenes Borane-carhonyl (B4H8CO),3295-297 bcnzoannulatcd systems, 25218-219 Borane complexes, 3251 degradation of horatabenzene metal Borancdiylhoriranc, reaction with stanny- complexes, 252 18 lene, 3Y:311 organotin route, 25217 Borane-metal complexes, 8:87-88 cobaltocene route, 25210, 216-217 Boranes, 39:364-368 complexes from boratabenzenes, B,OH derivatives, 3305-306 25219-220 BIzH12-derivatives, 3:305-306 complexes from boro-2.5-cyclohexa- as cluster fragments, 21:92-103 dienes, 25:220-221 equilibrium with diboranes, 3283 7-Borabicyclo[4.1.O]heptadiene. 39387 historical account, 1k1-18 Boracyclanes hydridic character, 2157 B-phenyl, 2271 isoelectronic, 3k219-225 by displacement, 2281 as ligands, 21:71-92 limit of reversible thermal isomerization, hydrocarbon analogs, tk71-80 22655271 and metal clusters, 2158-59, 92 by pyrolysis from alkylboranes, phosphine adducts, 9:300 2284-286 polytopal rearrangements, 16:341 Boracycloalkene, 39:357 rcduction of acyl complexcs, 1269-70 Boracyclodiene metal complexes, structure and honding, 15239 18309-310 third-order nonlinear optics, 43385, 391 Roracycloheptadiene systcms, 39387-388 Borasiloxane, 9:273-274 Bora-2,S-cyclohexadienes, borahenzenc Boratahenzenes, borahenzenc complexes complexes from, 29220-221 from, 23219-220 Boracyclohexenes, 131 56 Borataethenes, 39370-372 Boracyclopolyenes, 39357 Boratetralins, 2292-294 boracycloheptadiene systems, 39:387-388 dimcrization tendency, 2310 borepins, 39385-387 Bora-S,6.7-trihydroborepnylrhodiumcom- borircnes. 39359, 375-378 plex, 18310 boroles, 39380-383 Borazines, l&303, 39:24 boron derivatives of six-membered rings, analogy with benzene, 18:320 39384-385 exchange of suhstituents, 6:213 dihydroboretes. 39379-380 Group VI tricarbonyl complexes, dihydrodiboretes, 39:379-380 18320-321 hyperconjugation, 39574-375 a-Borazole-chromium complex, 8229 43 Boron heterocycles

Borazoles, hexaalkyl, chromium complexes, ethers, 8199 10:140 trihalides Borepin derivatives, 13192 reactions with sodium-potassium alloy, Borepin ring, 2273 10240 Borepins, 39385-387 synthesis of diboron tetrahalides from, Borinato complexes, 18315-320 10239 analogy with benzene and cyclopentadie- ylid, 2:301-303 nyl complexes, 18:317 Boron-boron bonds cobalt, 18315 bond energies, 1&248 electron-transfer properties, 18315, formation by coupling reactions, 10240 317-320 Boron-carbon multiple bonds, 39355-358 via insertion into cyclopentadienyl boracyclopolyenes, 39357 ring, 18315 boracycloheptadiene systems, ring-transfer reactions, 18316-317 39387-388 reactions with nucleophiles, 18318 borepins, 39385-387 ring contraction, 18:318-319 borirenes, 39359, 375-378 Borirene derivatives, 13148-149 boroles, 39380-383 Borirenes, 39359,375-378 boron derivatives of six-membered Borohydrides rings, 39:384-385 of alkali metals, lk5-6 dihydroboretes, 39379-380 cyclopentadienylthorium, 9388 dihydrodiboretes, 39379-380 cyclopentadienyluranium, 9384 hyperconjugation, 39358, 374-375 organosubstituted, 3292-294 organoboranes organosubstituted, reductions, 3267 I-alkynylboranes, 39366-367 Borolanes allyl-and benzylboranes, 39360, alkyl exchanges, 2:260 368-369 B-halo, 2315-317 arylboranes, 39:367-368 B-phenyl, 2:272 diborane(4) derivatives, 39373-374 thermal isomerization, 2264-265 methyleneboranes, 39:371-373 Boroles, 18302, 39380-383 methyleneborates, 39370-371 carbonyl complexes, 18309 vinylboranes, 39356, 359, 364-366 triple-decker manganese complex, a-bonding, 3%359-364 18~325-326 Boron compounds Boron complexes with metal carbonyls, 5129 halides, reactions with organometallic, 397 carbene complexes, 1421-27 amides, 3924 CICCO~(CO)~,14118-119 arsenides, 398 cobalt carbonyl, 14109 phosphides, 3928, 33-35, 38 lithium complexes a-bonding, 392, 359-364 hydrogen-bridged derivatives, W441 reactions with alkenes and alkynes, methyl, M394-395 5237-239 organic derivatives, see Organoboron redistribution, 6:206-214 compounds Boron heterocycles rearrangement of organoderivatives, Lewis acidity, 18302-303 1667-91 as ligands, 18301-340 terphenyl derivatives, M.19-23 five-electron donors, 18314-320 trifluoride adducts, exchange reactions, four-electron donors, 18309-314 8199-201 six-electron donors, 18320-324 alcohols, 8:199-200 three-electron donors, 18307-309 amines, 8200 metal complexes Boron heterocycles 44

bonding, 18304-307 molybdenum, 3:204,209 dinuclear, 18324-333 tungsten, 3204, 209 mononuclear, 18307-324 Bridged germylene complexes, see tetra-decker sandwiches, 18335-336 Germylene complexes, bridged trinuclear, 18333-336 Bridged phosphine complexes triple-decker sandwiches, 18325-333 chromium, 3203-204, 209, 212 structures, 18302-303 cobalt, 3238, 243 synthesis with CxK. 28106-107 iron, 3225,234-235 Boron hydrides, 14145-150 manganese, 3214-215, 222 carborane (B,BeC,H, I NMe?), 9252 molybdenum, 3:203-204,209.212 organoberyllium derivatives, 9251 nickel, 3249 structural relationship with high nucle- tungsten, 3203-204, 209, 212 arity metal carbonyl clusters, vanadium, 3195 14337-339 Bridged silyene complex, see Silyene com- Boronic acids, 10243 plex, bridged Boronium ions, 10:2S5 Bridging, in alkali metal organics, 27:177- Boron-metal clusters 178,213 based on Bridging ligands, hi- and trimetallic com- honiocuclear trimetal units, 335-18 plexes, 32219-310 homonuclear dimetal units, 33:2-5 a-alkyl/lr-alkene complexes, 32224-23s homonuclear tetrametal units, 3318-32 a-alkyl/a-alkyne complexes, 37:246-265 interstitial boron atoms, 3334-36 a-alkylh-ally1 complexes, 32235-246 mixed metal frameworks. 3333-34 a-benzenelu-alkyl complexes, 32292-300 bond distances, 3341-47 a-benzene/a-carbene complexes, NMR data, 3337-40 32300-301 Boron, s complexes s-benzene/cT-carbyne complexes, alkene complexes, 26:237-238 32300-301 as intermediates in hydroboration, mcarbene/n-alkene complexes, 26237 32266-270 cyclopentadienyl complexes, 26238-239 v-carbendn-alkyne complexes, dicarboll yl complexes, 26239-240 32272-275 as intermediates in organaborane re- a-carbeneh-ally1 complexes, 32270-272 arrangement, 26237-238 with carbon-hcteroatom a bonds, Boron-Wittig reactions, 39371 32301 -304 Borosilyl anion, 3846 ?r-cyclopentadienyllu-alkyl complexes, Boroxoles, 10:243 32275-288 Borthiinc, 18303-304 n-cyclopentadienyllu-carbene complexes, Group VI tricarbonyl complcxes, 18303, 32288-290 323-324 n-cyclopentadicnyllcT-carbyne complexes, Branched polymethylsilancs, photochemis- 32290-291 try, 1955 with pseudoaromatic heterocyclic s-li- Branched polystannane, 38215-217 gands, 32304-308 Branchiation intermediates, 3615-16 Bridging ligands, triosniiuni clusters, Brass, leaching by alkyl halides, 3873-74 268-38 Bridge bonds, in alkynylaluminum com- doubly bridging ligands, 2613-23 pounds, 26241 coordination geometries, 26:lY Bridged arsine complexes diastereomers, 2622 chromium. 3:204, 209, 212 double-atom bridge, 2616 iron, 3225, 234-235 bridged 0s-0s distance, 2616 manganese, 3214, 222 synthesis, 2616 45 Bulky

0s-0s distances, 2620 quadricyclane, 39:120 single-atom bridge, 2614-1 5 Buckingham potential, 36132 bridged 0s-0s distance, 2614-15 Bulk temperature, effect on sonochemistry, synthesis, -14-15 2989 structures, 2620 Bulky cyclopentadienes, concepts triple-atom bridge, 2617 chirality, 33347-351 bridged 0s-0s distance, 2&17 chiral character, assumption of, 33347 synthesis, 2617 R5C5-metal complexes, 33350-351 to increase nuclearity, 2667 (RlSC5)~Mcomplexes, 33351 mobility, -58-61 R'RZR3R4R5Cs-metalcomplexes, terminal atoms bridged, 268-13 33349-350 bonding modes, -9 kinetic stabilization, 33317-326 synthesis of, 269 air-stable compounds, applications of, triply bridging ligands, 2623-38 33324-326 five-electron donors, 26:32-37 antitumor agents, 33324-325 four-electron donors, 2625-32 charge delocalization, 33322-323 seven-electron donors, -38 decabenzylgermanocene, 33319 six-electron donors, -36-38 decaphenylmetallocenes, 33321 three-electron donors, 2624-25 decaphenylstannocene, 33320 Broadband decoupling, using multiple dose relationships, 33325 pulses, 28423-424 Mossbauer parameters, 33323 Bromides NMR spectra, 33323 alkyl, 28101 organometallic liquid crystals, allylic, 28119 33325-326 Bromination, terphenylbenzene, 44:56-58 pentaphenylcyclopentadiene, Bromine, reactions with unsaturated germa- 33:319-323 nium compounds, 39292-293 stereorigidity, 33320-322 cp-Bromo-1-alkanes, 3873 tetraphenylcyclopentadiene, 33319-323 Bromocyclotetrastannane, 38225 thermodynamics vs. kinetics, 33:3 18 Bromodiaminosilanes, 39187 novel molecular structures, 33326-342 Bromodiphenylarsine, structure, 4201 debenzylferrocene, 33339 2-Bromoethyl-diethyl phosphonate, decabenzylmetallocenes, 33337-339 38164-165 decaphenylferrocene, 33333 7-Bromoheptanenatrile, reaction with cop- decaphenylgermanocene, 33332 per, 3874 decaphenylplumbocene, 33332 1-Bromoterphenyl, perfluoronated, synthe- decaphenylstannocene, 33328-332 sis, M57-58 frontier orbital stabilization, 33331 Bronsted acids hexakis( trimethylsilyl)ferrocene, and Ni(0) complexes as catalysts, 33340-341 17:113-114 hexakis( trimethylsilyl)magnesocene, reactions with anionic transition metal hy- 33340-341 drides, 2233-34 orbital diagram, 33336 Bronze, leaching by alkyl halides, 3874 pentabenzylcyclopentadienylindium, Brook silenes 33337 properties, 3994-95 pentabenzylcyclopentadienylpotassium- reactions with tns(), 33337 aromatic ketones, 39125 pentabenzylcyclopentadienylthallium, carbonyl compounds, 39124 33334-337 dienes, 39117 pentakis(penty1 benzoate)cyclopenta- imines, 39:126 dienylthallium, 33328 Bulky cyclopentadienes 46

pentamethyl ketone, conversion of, reactions 33327 cocyclization with coordinated qui- pentaphenylstannocene, 33332 none, 12182 tris(trimethylsi1y1)cyclopentadienylin- with gerrnenes, 4126-127 dium, 33341 with lithium alkyls, 63 tris(trimethylsilyl)cyclopentadienyllith- oxidation by palladium(I1) salts, ium, 33339-340 12181 - 182 tris( trimethylsi1yl)cyclopentadienylthal- addition of acetic acid, 12181 ium, 33:341 with silenes, 39112-118 rotation dynamics, 33342-346 reactions with metal atoms, 1568-70 C5-M rotations, 33342-345 of main group elements, 1368-69 C5-substituent rotations, 33:345-346 with nickel, 1570 Bulky cyclopentadienyl metal complexes oligomerization, 1570 synthetic methods for, 33310-316 1,3-Butadiene tabulation of, 33352-379 codimerization Burg-Hurd hydroboration reaction. 368 with sorbic ester, 872 Burgi-Dunitz trajectory, for M + C-H=C- with substituted 1,3-dienes, 872-74 M-H, 28318 co-oligomerization Burg-Schlesinger diborane synthesis, 367-8 with acrylic esters, 876-80 [ (p-BuSe)Fe~(CO)&(p4-Se)],synthesis and with butyne, 863-67 structure, 4k275-276 with ethylene, 8.59-63, 80 (Bu,Sn),Te, synthesis, 42399-400 with styrene, 875-76 Butadiene cyclodimerization, 8.54-59 catalyzed reactions cyclotrimerization, 850-54 codimerization with ethylene, nickel-catalyzed dirnerization, 16145 12269-318 in photochemical reactions with metal by nickel complexes, 12142-146 carbonyl complexes cocyclization, 12142-146 of chromium, 26:298, 325-327, 329 cooligomerization with function- with decacarbonyldimanganese, alized olefins, 17:143 26:353-3.54 cyanation, 12224-225 with decacarbonyldirhenium, 26367 cyclization, 17:142 of molybdenum, 26:299,336-340,345, cyclotrimerization, 19286 347 dimerization, 19.287 of tungsten. 26299, 341, 351 oligomerization, 17:143, 199 synthesis of open-chain oligomers, polymerization, 12216-217 880-82 telomerization, 12143 ,r14~l,3-Butadienecarbonylmethyl-~s- by palladium complexes, 12141-193 pen tamethylcyclopentadienylmolybde- with carbon dioxide, 12178-179 num, 26337 cocyclization, 17:176-178 Butadiene complexes, 392, 103 comparison with nickel, 12143-146 theoretical studies, 1527-30 cooligomerization with olefins, $-Butadhe complexes, '.'C NMR spectra, 12179-80 19273, 275-278 oligomerization, fE148-150 Butadiene iron tricarbonyl, k2-5. 12, 29 telomerization, 17:151-168 mass spectra of derivatives, 6306, 312 use of telomers in natural product mass spectra of substituted derivatives, synthesis, 12182-189 8265-269 cyclodimerization via supported nickel (1,2,3-vl)-trans-Butadienyl complexes, in vi- catalysts, 15226 nylketene, synthesis, M290-294, 296 hydrogenation, 28107 p-,r14'-2-Buten-l,l-diyltetracarbonylbis($- 47 Calcium

cyclopentadienyl)ditungsten, synthesis, 40:224-225,228-230 26:351-352 carboxylates 1-Butene physical properties, 40:295-296 hydrogenation, 28107 synthesis, a291 isomerization, %lo8 chemical vapor deposition Butene l,4-diones, synthesis, 4k224 alkoxides, 40:250,253, 263-265, 315 tert-Butoxyl radical P-diketonates generation, U.83, 85 fluorinated compounds, 40:315-316 reaction with Lewis base adducts, 40.319-320 Ge hydrides, &88, 90 metal oxide film precursors, Sn hydrides, &99 40~317-319 tert-Butylacetylene, 3R68 monodentate donors, 40:320 t-Butyl isocyanide, nickel complex, 1k70 polydentate donors, 40.320-324 t-Butyllithium, reactions carboxylates, 40:324-325 addition to vinylhalosilanes, 3977, 93, cyclopentadienyl compounds, 40:311 105 thiocarboxylates, 40:326-327 with doubly bonded germanium com- diacetamide compounds pounds, 39293 physical properties, 40:296-297 with tin doubly bonded compounds, synthesis, 4&291-292 39313 dicyclopentadienyl n complex, 26:237 tertButy1 radical, reaction with Sn hy- P-diketonates drides, &97-98 crystal structures, 40:276-278, 280, 282 terf-Butyltrichlorosilane, 3R16 mass spectrometry, 40:282-283 physical properties, 40:265-271, 275, 281 C polydentate compounds Cacodyl, 4:145-146, 13:4 crystal structures, 40:286, 289 Cacodyl , 9170 mass spectrometry, 40:289-290 Cacodylic acid, 13:5, 3872 physical properties, 40:284-285 Ca[C(SiMe.& synthesis, 43285 synthesis, 40:283-284 Cadmium synthesis, 40:273-275 alkyls, bond dissociation energies, 2105 types, 40:272 borane complexes, 21:65 volatility, 40:281, 283 1,4-diaza-l,3-butadiene complexes, P-ketoiminates 21:167, 193 physical properties, 40265-271 mixed alkali metal compounds, 2R220, types, 40:272 256 metabolism, effect of silicon, 18:276 trimetallic complexes, 32287 metallocenes Cage compounds, polyhedrances with sili- crystal structures, 40:243-244, 246-249 con, germanium, and tin, 37:l-36 gas-phase electron diffraction, 40246 Calcium Lewis base removal, 40:237-238 alkoxides mass spectrometry, 40:246 crystal structure, 40255,261-263, 265 physical properties, 40:239-243 NMR, 40:263 stability, 40.236-237 physical properties, 40:255-259 synthesis, 40:237-239 synthesis, 40:253-255 mixed alkali metal compounds, 27:221 amides monocyclopentadienyl compounds crystal structures, 40:230-231, 234-236 physical properties, 40:297-298 physical properties, 40:226-227, 230, synthesis, 40:292-293 232, 234 phosphides Calcium 48

crystal structures, 40.230-231, 234-236 dimerization via hydrogen bonding, 18:28 physical properties, &226-227, 230, Hofmann acid amide degradation, 18:24- 232, 234 27, 30 synthesis, 40:224-225, 228-230 Carbamoyl complexes, 10122 polydentate ligands oxygen abstraction, 2267-68 crystal structures, 40.302, 304-305, 307, Carhamoyls 309 characterization of complexes, physical properties, 40:299-301 28155-157 synthesis of compounds, 40.298-299 decomposition of, %I86 poly(pyrazoly1)borates formation, rate law for, 28170 physical properties, 40:250-2.51 spectroscopic data, 28151-155 structures, 402.50 structural data, 28:150-152 synthesis, &249-250 synthesis of, 2&149-150 reaction atoms with alkyl halides, of Carbanions, 2128-132 1579 alkali metal complexes, without carbon- selenolatcs metal interactions, 27:239-260 physical properties, 40.293-295 Carbene complexes, 7:197, 14:2-20, 24-28, synthesis, 40:290-291 20:160-161, see also p-Methylene com- sulfonates plexes physical properties, 40:295-296 acidity of a-carbon atom of alkoxyalkyl- synthesis, &291 carbenes, 1413 thiocarboxylates physical properties, 40:295-296 addition reactions to low synthesis, 40:291 valent complexes, 20183-184 zeolites, 27:237 to metal-metal double bonds, 20184 Calcium-graphite intercalation compounds, addition-rearrangement reactions, 1413 2897 with hydrogen halides, 1413 Calorimetric studies, on arenechromium tri- analogy with olefins, 18232-233 carbonyls, 1356 in bicyclobutane rearrangement, 12466 Camphenilone, organomcrcury derivatives, bonding, 14:4-6 1023 bonding models, 25123 Cannizzaro reaction, 3571-72 carbene fragment, 25123 Carbaborane tigdnd charge distributions, 25124 B-H-metal bridge tungsten complex, coordination to a metal, 25123-124 31:64-70 geometries of, 25124-125 cobalt, 31:69 substituent effects, 25124 iridium, 31:67 carbene transfer reactions, 20188 molybdenum, 3k64-65 I3C chemical shifts, 12:143, 171 ruthenium, 3k63-64, 68 cluster formation with metal nucleo- tungsten-metal unsaturated bonding, philes, 18231-233 3k65 electron-transfer reactions, 235, 8-9, 28 nonspectator ligand, 3k62-84 gold(I), 2059-61, 64 spectator ligand, 3k59-63, 69-70 gold(III), 2086 Carbaboranes, 26:240 bis(carbene) structure, 20:97 Carbalumination, via rearrangement of or- 'H NMR spectra, 20212 ganoalanes. 16:98-106 hydrogenation of tungsten carbonyl deriv- Carbamoylcarbonyl complexes ative, 1292 from amines and metal carbonyls, as intermediates in sulfur dioxide inser- 1823-33 tion reactions with cyclopropyl com- cyclopentadienyls, 1827-33 plex, a57 49 Carbene complexes

iridium, nonheteroatom-substituted (alkyl- by substituents, 25142-146 idene) "C NMR studies, 146, 133 d*-alkylidene complexes, 25156 in olefin metathesis, 12449-489 reactions with OsC1(NO)(PPh3)3, organosilyl derivatives, 13119 25156-157 osmium reactions with substrate complexes, N-, 0-,S-, and Se-substituted, syn- 251 57-158 thesis d'-alkylidyne complexes from electron-rich olefins, from carbyne complexes, 25159-160 25140-141 from hydroxy-, alkoxy-, and halo- electrophilic addition to coordinated methyl complexes, 25160-161 imidoyl, acyl, thiocyl, dithioes- carbene ligand conformation, 25163 ter, and diselenoester ligands, carbon-metal bond, 25162-163 25135-138 chalcoformaldehyde complexes, 25166 from halogenocarbene complexes, electrophilic addition reactions, 25142 25164-166 nucleophilic addition to coordinated gold adducts, 25166 isocyanide and vinylidene Ii- nucleophilic addition reactions, gands, 25138-140 25167-168 from organic salts or salt-like re- reactivity, 25164-168 agents, 25141-142 spectroscopic properties, 25163-164 nonheteroatom-substituted (alkylidene) structure, 25161-163 d*-alkylidene complexes, 25156 sulfene complexes, 25:166 d6-alkylidyne complexes synthesis, 25156-161 from carbyne complexes, trans influence, 25163 25159-160 IR spectral studies, 145-6 from hydroxy-, alkoxy-, and halo- from isocyanide and alcohols, 1k40, 46 methyl complexes, 25160-161 liberation of carbene ligand, 1414-21 d'-alkylidyne complexes by acid, 1414-16 reactions with OsCl(NO)(PPh3)3, by 0, S, or Se, 1417 25156-157 by pyridine, 1416 reactions with substrate com- thermally, 14:36 plexes, 25157-158 trapping of ligand, 1415 carbene ligand conformation, 25163 ligand as nucleophile, 1293 carbon-metal bond, 25162-163 in Fischer-Tropsch synthesis, 17:93 chalcoformaldehyde complexes, mass spectra, 8:234 25166 from metal and olefin, 12457 electrophilic addition reactions, N-, 0-,S-, and Se-substituted, synthesis 25~164-166 from electron-rich olefins, 25140-141 gold adducts, 25166 electrophilic addition to coordinated nucleophilic addition reaction, imidoyl, acyl, thioacyl, dithioester, 25167-168 and diselenoester ligands, reactivity, 25164-168 25135-138 spectroscopic properties, 25163-164 from halogenocarbene complexes, structure, 25161-163 25142 sulfene complexes, 25166 nucleophilic addition to coordinated synthesis, 25156-161 isocyanide and vinylidene ligands, trans influence, 25163 25138-140 in peptide synthesis, 1411-12 from organic salts or salt-like reagents, in photodecomposition of metallacyclobu- 25141-142 tane, 12457 Carbene complexes 50

of platinum(IV), 22159-160 reactions with substrate com- polarization of M-C bond plexes, 25157-158 in tantalum derivative, 12462 carbene ligand conformation, 25163 in tungsten carbonyl derivative, 17:463 carbon-metal bond, 29162-163 positive charge on cu-carbon atom, 1414 chalcoformaldehyde complexes, reactions 25166 with acids, 1414-16 electrophilic addition reactions, addition at carbene carbon, 149 29164-166 with amines, 1411-12 gold adducts, 23166 carbene displacement, 1410 nucleophilic addition reactions, carbonyl substitution, 149-10 25167-168 with electophilic carbenes, 1420-21 reactivity, 25164-168 149-10 with phosphines, spectroscopic properties, 25163-164 1416 with pyridine, structure, 25161-163 substitution at carbene carbon, sulfene complexes, 29166 1411-12 synthesis, 25156-161 with vinyl ethers, 1417-18 trans influence, 25163 with N-vinyl-2-pyrrolidones, 14:18-19 substitution of hydrogen at a-carbon reactivity patterns, 25:325-126 atom, 1413- 14 effect of metal basicity, 23127-129 deuterium exchange, 1413 with electrophiles, 25127 synthesis, 143-4, 6-8 with nucleophiles, 25126-127 relationship with ylide complexes, 14240 from alcohols and isocyanide com- 147 of rhodium in hydrosilation, 12433-434 plexes, 147 ruthenium via carbene transfer, N-, 0-,S-, and Se-substituted, syn- via cleavage of electron-rich olefins, thesis 148 from electron-rich olefins, from 1,l-dichloro-2,3-diphenyl-2-cyclo- 25140-141 propene, 146 electrophilic addition to coordinated via organolithium reagents, 143-4 imidoyl, acyl, thioacyl, dithioes- in synthesis of p-methylenes, 20184-188 ter, and diselenoester ligands, of tantalum, decomposition to give ethyl- 25135-138 ene complex, 17:92, 461 from halogenocarbene complexes, X-ray structural studies, 14:4-5, 7 25142 ylide formation, 12463 nucleophilic addition to coordinated d-Carbene complexes, carbonyl insertion, isocyanidc and vinylidene li- M288-289 gands, 25138-140 Carbene insertion, into palladium-chlorine from organic salts or salt-like re- bonds, 13371 agents, 25141-142 Carbene ligands nonheteroatom-substituted (alkylidene) from ketene transformation, 28:ll-13 d'-alkylidene complexes, 25156 Carbene ligands, computer representation db-alkylidyne complexes conversion to olefin, %181 from carbyne complexes, coupling, 26178 25159- 160 electrophilic addition, 26193 from hydroxy-, alkoxy-, and halo- hydride extraction, 26193 methyl complexes, 25160-161 I+-Carbeneln-alkenc bi- and trimetallic com- dx-alkylidync complexes plexes, 37:266-270 reactions with OsCI(NO)(PPh,)3, o-Carbeneh-alkyne hi- and trimetallic com- 25156-157 plexes, 32272-275 51 Carbon-13 chemical shifts a-Carbeneh-ally1 bi- and trimetallic com- Carbocycles, structures, 13224-225 plexes, 37270-272 Carbocyclic olefin complexes, 353-62 Carbenes, 3950 Carbodiimide, see Cyanamide amino, chromium complexes, 10165 Carbohydrate, synthesis of substituted al- analogy with titanocene, 193-4, 6 kenylcarbene complexes, 4k216-218 condensation of hydroxy species in Fi- Carboimines, 39:181 scher-Tropsch reaction, 1786-87 s-Carbollyl (BloCHIl3-)complexes, -germylene coupling reactions, a116 8100-101 from a-heterodiazoalkanes, 8410 Carbon insertion reactions, 8421-424 -heteroatom, triple bonds, M191-192 metal-carbon bonds, 9415,421 -hydrogen bond, phosphinocarbene inser- metal-halogen bonds, 8421 tion, 44.192-193 metal-hydrogen bonds, 9423 s complexes, 26:257 metal-oxygen bonds, 9423 terphenyl derivatives, &31-32 reactions with transition metal com- Carbon-carbon bond pounds, 8422,424 formation insertion into copper-carbon bonds, via organocopper compounds, fi230 12254-259 metal, 28:22-26 via organonickel complexes, rearrangement to olefins, 196 17198-234 in vinylketene synthesis, M298-300 formation of CsK, 28105-106 Carbenoids scission and of CsK, 28:105-106 classification, 12:84-85 Carbon-carbon double bond, reduction, copper, 12:309 38172 zinc, 1284-102 Carbon-carbon triple bond, a80 Carbenoid species, reaction with phosphino- bond distances, 38100-105 carbenes, M197-199 reduction, 38172 , 8271-272 stretching frequencies, 38:121-138 as intermediates in Fischer-Tropsch reac- Carbon-centered radical, reactions tion, 1786-87 with Ge hydrides, M86, 88 Carbidocarbonyl clusters, 221-58 with silicon hydrides, M.74, 77, 79-81 I3C NMR spectra, 2246-48 with Sn hydrides, M90-91, 94-99 chemical shifts, 2247 Carbon-13 chemical shifts, 12:140-155 reactivity of carbide ligand, 2251-55 Ir-acetylene complexes, 12:153, 184 source of carbide ligand, 2248-49 acetylide derivatives, l2:145-146 from carbon halides, 2249 a-allyls, 12:153-154, 185 from carbon monoxide, 2248 u allyls, l2:178 structures, 2249-51 s-arenes, 12:155, 189 effective radius of carbide, 2250 s-bonded carbon atoms, 12152-155 vibrational spectra, 2245-46 u-bonded carbon atoms, 12:140-152 metal-carbide stretching frequency, carbene complexes, 12:143, 171 2246 chromium compounds Carbido clusters carbenes, l2171 bonding, M73 carbonyls, 12173 comparison with nitrido clusters, 2469, (s-C6H6)2 Cr, 12:152 73-74 (s-CgH6) Cr (co),, el52 fluxionality, X76 a-cycloheptatrienyl complexes, 12155, NMR spectra, M74-76 189 Carbocations, resemblance to metallic a Ir-cyclopentadienyls, 12:186-188 complexes, 26257 a-cyclopentadienyls, el79 Carbon-13 chemical shifts 52

dienc complexes, 12:154, 185 palladium-catalyzed reaction with butadi- ethyl compounds. 12145, 177 ene, 12178-179 fluxional molecules, 12146-150, 190 mechamsm, 12179 iron carbonyl derivatives, a176 2-pyrone formation, 22162 methyl complexes, n140-141, 166-169 reaction with molybdenum carbonyl derivatives, a174 ally1 complexes, 22159, 161-163 olefin complexcs, 12:153, 184 dicarbonyldicyclopentadienyltitanium, organolithium compounds, a142-143 19:38 paramagnetic compounds, 12:151-152, reduction to CO by metal cornplexcs, 183 22154-156 phenyl complexes, 12.141-142, 170 electrocatalysis, 22156-157 relationship with Cotton-Kraihanzel force Walsh diagram, 22133, 135 constants, U.144-145 Carbon diselenide ruthenium complexes, 12172 head to tail coupling, 3269 tungsten carbonyl derivatives, a175 heterometallacyclcs, 3264 vinylic complexes, 12145, 177 reaction Carbon dioxide addition, 3267-68 activation by metal complexes, dimerization, 3269-70 22129-168 insertion, 3264 catalyzed reactions Carbon disulfide alkylformate ester formation, 22157 alkylation, 3266, 68 co-oligomerization with allenc, 22162 cluster complex, 32x55-66 with hydrosilanes, 22163 coupling reactions with germylene, coordination chemistry, 22131-136 44A15-116 v2-C,0-bonding, 22131-132, 134 cycloaddition, 3266 q'-C-bonding, 22132 formation, dithiocarboxylate, 3262, 64 ligand effects, 22136 head to head coupling, 32:71 v'-0-bonding, 22131, 134 head to tail coupling, 3269 X-ray structures, 22131-136 heterometallacycles, 3264 effect on butadiene reactions insertion into dimerization, 12178 metal-carbon bonds, a74 telomerization, 12151-152, 178 metal-hydrogen bonds, 22138 extrusion from mctalloformates, 22138 platinum-hydrogen bonds, 13305 hydrogenation, 22158 reaction insertion into metal-carbon bonds, 1273. addition, 3266-68 22145-151 dimerization, 3269-71 slereochemistry, 22150 insertion, 3262-66 insertion into mctal-hydrogen bonds, thiocarbamate complex, 32:63 22136-145 Carbon-germanium bond formation analogy with alkene insertion, double germylation, 43219-220 22:137-138 gcrmylstannation, 43223-224 of anionic Group 6B pentacarbonyls, hydrogermylation, 43200-201 22138-139 Carbon-halogen bond metallacarboxylic acid formation, bond energy, 3862 22137 dihalo- and monohalocarbene complexes inscrtion into metal-nitrogen bonds. of Os, lr, and Ru, 25173 22152-153 dipole moment, 3860 insertion into metal-oxygen bonds, scission, 3863-64 22:lSI-152 Carbon-hydrogen bonds lactone formation. 22161 in agostic species, 28300 53 Carbon monoxide

lengthening from agostic interaction, metal-coordinated nucleophile adducts 28319 of, 28139 as ligands, 2&317-332 nucleophilic activation by WGSR ca- Carbonium ions, 2129, 131 talysis metal complexes, 8137, 146-1.56 acidic solutions, 28191, 196-197 nonacarbonyltricobaltcarbon substituted, alkaline solutions, 28187-194 14119-134 aqueous organic amine solutions, stability of ferrocenylmethyl, 14131 28190, 194-195 Carbonium ion-type ligands, k3-4, 11, 30- neutral solutions, 28191, 196-197 31,33-35 polynuclear 11-bonded compounds, Carbon-metal bond, 38105-116,136-137 23275-279 alcoholysis, 28:184-185 heteronuclear, 23276-278 of nonheteroatom substituted Os, Ir, Ru reactions with carbene (alkylidene) complexes, a~etylcarbonyl-~~-cyclopentadiene-~- 25162-163 cyclopentadienylmolybdenum, Carbon monoxide 26344 bimetallic complexes, 32302-303 1,3-ditungstacyclobutadienes, dissociation from carbonylmetal com- 26116-118 plexes, M149-150 metal atoms, 1363 dual coordination in Fischer-Tropsch re- pentadienyltricarbonylmanganese com- action, 1275 plexes, 26150 edge-bridged 8-bonded complexes, potassamide, 1822-23 tungsten alkoxides, 22358 23245-256 reactivity, 23279-296 alkali metals, 23248-249 reduction to methanol when bonded to carbocations, 23249-251 zirconium, 19:38-39 Group 111 derivatives, 23251-256 rheniumpentacarbonyl alkyl reaction, hydrogen-bonding acceptors, 32210 23257-258 ruthenium allenyl complex reaction, lanthanides, 23251, 254-256 32122 protons, 23245-247 terminal R-bonded complexes, 23228-245 exchange reaction with oc-alkynedicobal- alkali metals, 23228-235 thexacarbonyl complexes, 12:340-343 aluminum derivatives, 23:238-241 face-bridged S-bonded complexes, Group 111 derivatives, 23238-241 23257-267 hydrogen-bonding acceptors, 23228 alkali metals, 23258-260 lanthanides, 23238-241 Group I11 derivatives, 23260-264 magnesium ions, 23:235-237 Group IV derivatives, 23264-266 transition metal adducts, 23242-245 hydrogen-bonding acceptors, Carbon monoxide, C- and 0-bonded to 23:257-258 metals, 23219-305 transition metal adducts, 23267 assisted migratory insertion, 23279-288 insertion into Mo-AI bond, and olefin by amphoteric molecules, 23:286-287 metathesis, 12455 by cations, 23281-282 insertion reactions, 5302-305 by Lewis acids, 23282-288 effect of sulfur dioxide, a36 by protons, 23281 intramolecular insertion, 5306-309 bonding modes, 23219-227 manganesepentacarbonyl alkyl reaction, cleavage and reduction reactions, 32197-1 98 23:288-292 mediated electron-transfer reactions, dinuclear 11-bonded complexes, 23:292-296 23~268-275 Carbon monoxide 54

structures, 23270-271 double silylation Carbon monoxide, insertion into metal-car- catalysts, 43211-212 bon u bonds, 1k87-139 dehydrogenative double silylation, cobalt complexes, 1k131-133 43217-218 cffcct of alkyl group, 11:101 dimerization-double silylation, a212 intermediates, 1k97 mechanism, 43:208-210 iron complexes, 1k126-130 phenyldisilanes, 43:210-211 kinetics and mechanism, 1k94-104 substrate reactivity, 43209, 213-214 ligand effects, 1k99, 102 terminal alkyne substrates, 43215-216 manganese and rhenium complexes, hydrosilylation, 43199-200 1k122-126 silyl group transfer between olefins, molybdenum and tungsten complexes, 43207-208 1k118-122 silylstannation, 43221-223 nickel, palladium. and platinum com- Carbon-tin bond formation plexes, 1k137-139 double stannylation, 43220-221 rhodium and indium complexes, germylstannation, 43.223-224 1k133-137 hydrostannylation, 43200-202 ruthenium and osmium complexes, silylstannation, 43221-224 1k130-131 Carbonylation, 5230-231 solvent effects, 1k97 acetylenes, 23-4 Carbon monoxide laser, for IR kinetic spec- alkynes, 23-5 troscopy, 23291 ally1 chloride, catalyzed by supported Carbon monoxide-metal complexes, 38114 complexes, l5:223-224 Carbon-nitrogen-phosphorus polymers, allylic chlorides, 38:175 32133 aryl halides, 28 Carbon-oxygen bond activation carbenes, 29 allylic oxygen bond cleavage catalytic, 32170 non n-ally1 complexes, 34:124-129 diazonium salts, 2:9 8-ally1 complexes, 34113-123 gem-dihalides, 29 carbon-oxygen cleavage manganese alkylpentacarbonyls, 32173- concerted processes, M.129- 139 174, 192, 198,213 two-step mechanisms, 34139-140 of metal carhenes by ketene complexes, C=O cleavage 2822-26 aldehydes, 34240-143 in metal-induced conversion of ketenes esters, 34:140-143 into other organics, 2815 ketones, M140-143 methanol, 12255-267 Carbon-ruthenium bond, 3888-89, 104, 114 by cobalt catalysts, 12256 Carbon-silicon bond formation by iridium catalysts, 12264-266 1,l-additions of oligosilanes to isonitriles, comparison with rhodium, 12264 43224-225 mechanism, 12265 dehydrogenative silylation reactions by rhodium catalysts, 122.57-264 allylsilane substrates, 43206 formation of active species, 12258 a,P-unsaturated esters, 43204 kinetic studies, 12257 catalysts, 43203-204, 206 promotion by halides, 12261-262 l,S-dienes, 43204 reaction cycle, 12258-259 divinylsilane substrates, 43:205-206 side reactions, 12262 ethylene, 43204-205 on support, 12262-264 fate of hydrogen, 43203 of nucleophile-carbonyl adducts, 28144, styrene, 43205 148 terminal alkyne substrates, 43207 under WSGR conditions, 28203-205 55 Carbonyl compounds

olefins, 26 dienyl) discarbonylhafnium forma- oxidative, of alcohols to dialkyl oxalates, tion, 25341-342 28205 (q-C5Me5)CpM(CO), preparation, reactions, catalysis by CO~(CO)~, 25342 6158-163 containing 7-arene rings, 25375-376 in synthesis of ketenyl complexes, containing one v5-C5H5ring, 28:57-59 25374-375 via organonickel compounds, 12225-234 containing a-bonded acyclic hydrocar- Carbonylcobaltate(-I), and carbonylco- bon chains, 25:3?2-374 balt(I), coupling, 3376-79 formation with other $-rings, Carbonylcobalt ion pair dimers, 3377-78, 25342-346 82-83 functionally substituted q-cyclopenta- Carbonyl complexes dienyl dicarbonyl complexes of Ti alkali metal carbanions, 22246-250 and Zr, preparation, 25345-346 anionic transition metal hydrides 'H NMR spectra, 25348-350 as catalysts, 2244-46 IR spectra, 25347-348 interaction with sodium ions, 2224 mass spectra, 25351 reactions, 2228 photoelectron spectra, 25351 with acid halides, aldehydes, and ke- physical properties, 25347 tones, 2241-43 structural properties, 25351 with alkyl halides, 2235-41 Group VI and VII metals, photochemis- with Bronsted acids, 2233-34 try, 26:297-375 with Lewis acids, 2230-33 molybdenum and tungsten alkoxides, spectroscopic properties, 224-7, 20-27 22359-364 structural characteristics, 2212-17 not containing p-bonded hydrocarbon li- binary, 23319 coupling of carbonyl rearrangement and gands, 25319-322 n-ligand rotation, 16:231-236 platinum(IV), 2R158-159 electron-transfer reactions, 234-34 redistribution reactions, 23109-111 Group 4B and catalyzed substitution, 23110-111 ansa-titanocene dicarbonyl derivatives, transition metal carbynes 25343-344 bonding, 27:52-53 bis( v-cyclopentadienyl) reactions, 2270-?9,82-89, 94-103 dicarbonylhafnium formation, structure, 2253-55 25336 synthesis, 2757-60, 63-69 bis( 7-cyclopentadienyl) trimethylenemethane metal complexes dicarbonyltitanium formation, reactions with 25322-333 electrophiles, 27:294-295 bis( 7-cyclopentadienyl) nucleophiles, 2x295-297 dicarbonylzirconium formation, tertiary phosphines, 22297-298 23333-336 structure, 22290 bis(q-indenyl dicarbonyl complexes of synthesis, 22280-289 Ti and Zr, 25342-343 Carbonyl compounds bis( v-pentamethylcyclopenta- addition to pentadienylmetal complexes, dieny1)dicarbonyltitanium forma- 26132 tion, 25336-338 insertion, 5228-231, 247-248, 291 -292 bis( v-pentamethylcyclopenta- reactions with dieny1)dicarbonylzirconium forma- doubly bonded germanium com- tion, 25338-341 pounds, 39295-298 bis( T-pentamethylcyclopenta- silenes, 39122-128 Carbonyl compounds 56

tin doubly bonded compounds, phosphine, 3375 39314-315 carbonylmetal cations, coupling with, Carbonyl derivatives, [ 1 + 21 cycloadditions, 3372-73 U190-191 electron transfer, 3383-87 Carbonyl exchange, 16323-332 ion-pair annihilation, rate of, 3386-87 in cyclopentadienyl iron dicarbonyl di- isomeric contact ion pairs, annihilation mer, 16323-325 rates of, 3385-86 and derivatives, 16324-325 Mn-Mn bonds, formation of, 33:84-85 mechanisms, 16326, 331-332 Carbonylmetallate ligand, 3960 in tetranuclear clusters, 16928-330 Carbonylmetallates, 811-12, 32230, 233, rhodium, 16328 23.5, 246 in trinuclear clusters, 16:326-329 polynuclear, 84, 6, 11 of iron group, 16326-329 Carbonylmetallite anions Carbonyl group electron donors, charge-transfer salts of bonding to metals, 3185 diffuse reflectance vs. absorption spec- insertion into v’-carbene complex, tra, 3359-60 44.288-289 IR spectra, 3358-60 Carhonyl ligands isolation, 3354-56 coupling reactions. computer representa- kinetics, 3366-69 tion, 26:179 photoexcitation, 3363-72 scrambling, in h4-dienemetal carbonyls, qualitative treatment, 3362-63 26304-307 reactive intermediates, 3365-66 Carbonylmanganate(-I), and carbonylman- solvatochromism, 3360-63 ganese(I), coupling, 3373-76 spectral characterization, 3354-56 Carbonylmetallate anions visible absorption bands, 3356 chromium, molybdenum, and tungsten, X-ray crystallography, 3356-57 3k39-46 thermal annihilation of cobalt, rhodium, and iridium, 31:31-38 added phosphine effect, 337578 manganese and rhcnium, 3k2-15 added salts, inhibitory effect, 3379 super-reduced species prospect, 3k47 carbonylcobalt cations, carbonylco- vanadium, niobium, and tantalum, baltate coupling with, 3376-79 3M5-31 carbonylcobalt cations and carbonylco- Carbonylmetallate anions, thermal annihila- baltate anions, spectral study of, tion of 33:79-82 carbonylcobaltate( -I) and carbonylco- carbonylcobalt dimers, formation, balt(I), coupling of, 3376-79 3382-83 dimers, 3377-78 carbonylmanganese cations, carbonyl- phosphine effect, 3378 manganate coupling with, 3373-76 salts, inhibition, 3379 Mn-Mn bond formation, mechanism, solvent polarity, 3378-79 3375-76 carbonylcobaltate(-I) and carbonylco- solvent polarity effect, 3378-79 balt(1) ion pairs Carbonyl methylidyne complexes, 2866 electronic spectra, 3379-82 Carbonyl migratory insertion reactions, IR spectra, 3382 23279-288 spectral study, 3379-82 Carbonyl polyhedron, in dodecacarbonyltri- carbonylcobalt dimers, formation of, osmium, 2640 33:82-83 Carbonyls, see also Cationic metal carbon- carbonylmanganatesf-I) and carbonyl- yls; Metal carbonyls manganese(I), coupling of, 3373-76 absorption, infrared, of dieneiron com- mechanism, 3375-76 plexes, M1, 30 57 Carbosilane synthesis

coupling with titanium-graphite, electron-withdrawing characteristics, 28126-128 3:337-354 derivatives of Pt(I1) and Pd(I1) perhalo- germanium insertion, 26266 phenyl complexes, synthesis of, Grignard reagents, 3321-322 28244-246 hypho compounds, see hypho-Carboranes dicyclopentadienyl titanium, 9:179 isoelectronic, 30220-221 formation from metal salts and alcohol, isomers, 3317-318 3~236-237, 247 Keilin synthesis, 369 Group VIII, water gas shift catalysis of, lanthanide chemistry, 36309-310 28:193 metal complexes, 14145-186 a,B-unsaturated, reactions of, 28:103-104 metallation, 3320-322 Carbonyl sulfide, insertion into metal-hydro- nido compounds, see nido-Carboranes gen bonds, 22138-139 nomenclature, 3631-32 Carborane, 3315-354, 24k240, 39356 phosphine derivatives, 3331-332, 343, acid derivatives, 3323-327, 340 346, 348-349 alkenyl derivatives, 3322-323, 339 polyborane, M17-18 arachno compounds, see arachno-Carb- polyborane Lewis base adducts, 36:30 oranes polyhedral rearrangements, 14146, 149 beryllium derivative, 9252 polymers, 3333-334 bonding, 3307-308 preparation, 3315-316 Burg-Hurd hydroboration reaction, M8 properties, 3312-315 Burg-Schlesinger diborane synthesis, rearrangements, 3:334 36:7-8 silicon derivatives, 3329-331, 341, 343- carbocations, 36:15-17 348, 350 Brachiation intermediates, 36:15-16 structure, 3264, 316-319 nonclassical structures, W15 and bonding, 15239 structures, 3615-16 determinations, 3610-13 chlorinated derivatives, 3319-320 thermal rearrangement of metal com- classification, 36.22-29 plexes, 16:341-342 geometrical systematics, M23-25 Carborane carboxylates, metal, thermal de- geometry, 3622-24 carboxylation, 25264 most spherical deltahedra, 3625-28 Carborane complexes, 29190-191 site preferences, 36:29 divalent tin and lead, 19:135-137 Wade's rules, 3624-25 Carborane-metal complexes, 887-1 13 classification, geometry, 30100-101 arsacarbollides, 8103-104 closo compounds, see closo-Carboranes B6C2H2-ligand, 8:111-112 conversion to dicarbaundecaboranes, B7C2Hg2-ligand, 8109-111 3332-333 carbollyl complexes, 8100-101 definition, 3264, 3099 dicarbacanastide complexes, 8112-1 13 degradation reactions, 14147 1,2-dicarbollyl complexes, 891-100 derivatives, 3383-353 1,7-dicarbollyl complexes, 8100 direct l3C-'H coupling constants, 12.164, nomenclature, 888 182 phosphacarbollides, 8101-103 early processes, 36:9-10 physical properties, 8104-109 electron counting, 3631 thiollides, 8:104 electron pair bonds, 36:18-21 Carbosilane polymers, 3986 Chop-stx, 3620-21, 31, 42 Carbosilane synthesis evolution, 3619 dehydrogenative coupling of trialkylsi- S~YX,36:19-21, 30, 32 lanes, 43225 electron processes, 36:9-10 transfer dehydrogenative coupling of trial- Carbosilane synthesis 58

kylsilanes in presence of olefins, reactions with 43:225-228 chalcogens, 25191 Carboxamido complexes, of manganese, electrophiles, 25190-192 1393 Group I metal halides, 25191 Carboxylate complexes halogens, 25192 as catalysts, 12332 nucleophiles, 25192-193 palladium protic acids, 25190 binuclear, 19.164, 166 sulfur dioxide, 25191 diene derivatives, 19164 structure, 25186-188 with metal-metal bond, l9:162-165, synthesis, 25181-186 176 vibrational spectroscopy, 25188-189 mononuclear, 19164, 166 reactions, 1428-29 Carboxylation reactions, 6157 reactivity patterns, 25131-134 Carboxylic acids carbyne carbon, 25133 reactions with unsaturated germanium carbyne substituent, 25133 compounds, 39292 effect of metal basicity, 25134 reduction with organotin dihydrides, electrophilic addition, 25133 k82-84 metal, 25:133 Carbyne-alkyne coupling reactions, nucleophilic addition, 25131-133 3272-73 synthesis, 14:21-28 Carbyne complexes via aluminum halides, 1427 addition reactions via boron halides, 1421, 24-26 to low valent complexes, 20183 via gallium halides, 1427 to metal-metal double bonds, 20184 transition metals, see Transition metal car- addition to byne complexes @unsaturated esters, 16307 X-ray structural studies, 1422-23 vinyl ethers, 16307 Carbyne ligands, coupling reactions, com- analogy with acetylenes, 18231-233 puter representation, 26:178-179 bonding models Car-Parrinello method, 36533 carbyne fragment, 25129-130 Catalysis complex formation, 25130 by alkylidynetricobalt nonacarbonyls, heteroatomic substituents, 23130 14~137-138 metal fragment variation, 25131 acetylene trimerization, 14137 substituent effects, 25130-131 olefin polymerization, 14137-138 cleavage of carbyne ligdnd, 1428-29 cluster, see Cluster catalysis cluster formation with metal nucleo- of cocyclization of acetylenes and isocya- philes, 18231-233 nides, 14:263-265 I3C NMR, 14:22 computers in, 26:165-216 chemical shifts of carbyne carbon catalyst representation, 26168-169 atom, 14:133 of cyclo-oligomerization of allenes, osmium and ruthenium 14270-278 cationic dRcomplexes, modification, by Ni(0) complexes, 14271-277 25184-185 by rhodium complexes, 14277-278 "C NMR spectroscopy, 25188 fluid bed, 15192 from dihalogenocarbenes, 25182-183 heterogeneous a-metalladiazoalkanes as precursors, of Fischer-Tropsch reaction, 1R62 25183-184 of hydroformylation, 1R47-53 oxidation of metal heterogeneous vs. homogeneous, by iodine, 25186 15190- 192 by oxygen, 25185 controllability, 15.191 59 Catalytic reactions with H2

efficiency, 15:190-191 nitrobenzene, catalytic cycle, 3548 reproducibility, 15191 nitro compounds, 3548-49 specificity, 15191 Monsanto acetic acid process, 35:44-45 thermal stability, 15:191 Catalytic reactions with CO and H2 homogeneous, see Homogeneous ca- hydroformylation, 3580-89 talysis chemoselectivity, 3580 by mixed-metal clusters, 18207-208, cyclohexene, mechanism, 3588 256-257 ethylene, catalytic cycle, 3586-87 of olefin and diene polymerization formaldehyde, 3589 alkyllithium initiation, 1855-97 mechanistic studies, 3587 Ziegler-Natta, 1899-149 olefin, 3580-85 of olefin metathesis, 16269-271, 283-317 regioselectivity, 3580, 86-87 oligomerization of acetylenes, 14262-263 miscellaneous reactions, 3593-95 of organic synthesis by nickel com- syngas reactions, 35:74-80 pounds, 848-83 catalytic systems, 3575 by organometallics, 10331-336 Fischer-Tropsch process, 3574 by rhodacarborane complex, 14183 hydrogenation of carbon monoxide, role of u-?Trearrangements, 16241, 3S76-79 252-271 Catalytic reactions with CO and H20 hydroformylation, 16266-268 hydroformylation using water, 3599-102 hydrogenation, 16263-266 hydrohydroxymethylation, 3599-101 olefin isomerization, 16:260-262 olefins, 35:1M)-101 olefin oxidation, 16252-256 Reppe synthesis, 3599 olefin polymerization, 16256-260 hydrogenation using water, 35102-104 Ziegler-Natta process, 16256-259 nitroaryls, 35102 by supported transition metal complexes, nitrobenzene reduction, 35103 15189-231 selective reduction, 35102 by transition metal alkyls (aryls), miscellaneous reactions, 35104-107 2197-204 water-gas shift reaction, 3595-99 carbonylation reactions, 2198 catalytic cycle, 3596-97 olefin dimerization and polymerization, CO exchange kinetics, 3597 2199-201 definition, 3595 olefin hydrogenation, 2202 equilibrium, 3597 olefin isomerization, 225 hydrogen formation, 3598 by triosmium clusters, 2663-65 Catalytic reactions of diazoalkanes, Catalysts, 2244-46 9424-426 0x0 reaction, 6136 decomposition, 9424 supported, see Supported catalysts polymerization, %424 Catalytic hydroformylation reaction Catalytic reactions with H2 catalysts, 6136 hydrogenation of isomerization, 6131 acetylenes, 35:60-64 mechanism, 6128-131 aldehydes, 3564 Catalytic reactions with CO alkynes, 3561-63 carbonylation of bis(triRuoromethy1) acetylene, mecha- alcohols, 3544-45 nism, 3564 amines, 3545-46 carbonic acids, 3566 heterocycles, 3546 carbonyls, 3564-66 deoxygenation of ketones, 3564 aldoximes, 3547-48 nitrogen containing functions, 35:67-68 ketoximes, 3546-47 olefins, 3549-60 Catalytic reactions with HZ 60

alkenes to alkanes, 3550-53 hydride abstraction, 8126-127 asymmetric, 3554-56 oxidation reactions, 8127-129 enantiomer discrimination, 3557 protonation, S:121-125 enantioselective, 3.555-56 titanium, 8131 ethylene mechanism, 3558-59 vanadium, S:131-133 maleic anhydride, catalytic cycle. Cavitation 3559-60 conditions, experimental determinations photocatalytic, 3549-54 of, 2581-82 selectivity, 35.54 in homogeneous media, 2976-82 orthoesters, 3566 nucleation of, 2575-76 hydrogen transfer reactions, 3567, 69-72 at surfaces, 2582-84 asymmetric reduction, 3570-71 Ceramics, iron ceramics, via Cannizzaro reaction, 3571-72 pyrolysis, 37:150-151 catalytic, 3567, 69 Cerium, reduction of cyclooctatetraene com- Schiff base reductions, 3569 plex, 2366 ketrachloromethane, mechanism, 3571 Cesium hydrosilylation reactions, 3572-73 benzenide salt, 16:200 Catalytic reduction of oxygen, by arene- metal-carbon bond lengths, 43342-343 metal complexes, 1350-51, 69 physical properties, 27974 Catenated compounds, 225 reducing properties, 16201 Catenation safety in handling organometallic com- carbon, 1:90 pounds, 43269 Group IVb elements, 1:90-91 salt of fluorene, 16201 tin hydrides, l50 solvation energy, 27:182 Catenation in Group IV elements, 41-84 Cesium, organometallic compounds definition, 4:l-2 structure determination, 43:268, 271-272, germanium, 43-47 342 lead, 463-77 synthesis and structures silicon, 42-38 alkene derivatives, overview, 43309, tin, 447-63 311, 326 trends, 4:82-84 alkylalkoxide intermediates, Cation association reactions, computer rep- 43291-292 resentation, 26180 alkyl group exchange, 43270 Cationic ligands, 1:3-4, 10-1 1, 30-31, alkyne derivatives, 43326 33-35 ally1 derivatives, 43311-313, 315-319 Cationic metal carbonyls. 8117-159 arene derivatives, 43326-332, 334-341 cobalt, 8152-155 azaallyl derivatives, 43319-320, Group VI metals, 8133-137 323-324 halogen-containing, 8127-128 azulene derivatives, 43307 iron, &I43 benzyl and realted derivatives, ligaiid substitution reactions, 8130 43271-275 manganese, 8137-143 cumyl derivatives, 43275, 277 phosphine derivatives, 812-13 cyclopentadienyl derivatives platinum metals, 8155-158 substituted derivatives, 43299-301, synthesis, 8119-131 304 alkylation, 8125 unsuhstituted derivatives, 43294- carbonylation, 8129-130 297, 299 disproportionation, 8120 fluorenyl derivatives, 43305-306 electrochemical, 8129 fullerides, 43341-342 halide displacement, 8119-120 indenyl derivatives, 43304 61 Chalcogens

methyl derivatives, 43271 alkyne derivatives, 4k274-279, 281, organolithium reagents, 43:269 283 reagents, 43269-270 formation under facile conditions, pentalene derivatives, 43308 4k271-272,274 phenyl derivatives, 43292-294 tetranuclear clusters, 4k265-266, silicon-substituted alkyl derivatives, 268-271 43:280,283-286,288-289,291 selenium ligand, 41:243-244 triphenylmethyl derivatives, 43:277, 280 structures, 4k244-248,250-253, 255-256, X-ray structural analysis, 22169-277 258-264,266-271,273,275-278, aggregation, 22180-181 280-288,290-294,296-305, 307-309 alkyls, 22191-192 tellurium ligand, 41:243-244 bond lengths, 27:186, 190 Chalcogen exchange, germaneselone, 44.159 bridging, 22178 Chalcogen-germanium bond, heterocycles, without carbon-metal interactions, 44~155-156 22240-243,245,250-252,254,256 Chalcogen heterocycles, 39:211 charge delocalization, 27:173 Chalcogenides, reactions, with transition coordination, 22176 metal carbynes, 2294-95 graphite intercalates, 27:206-207 Chalcogen metal carbonyl complexes, ionicity, 22176 819-20 mixed metal compounds, 22208-209. Chalcogenolates, terphenyl ligands, 44:53 212,218-220,226,228-229, 231- Chalcogens biselenide 232,235 Cesium graphite intercalation compound, alkylation, 3260 protonation, 3260 2896 bisulfide C$5X, arylation with, 2&228-229 alkylation, 32:60 Chalcoformaldehyde complexes, reaction protonation, 3260 with d8 alkylidene complexes of Ru, carbon diselenate Os, and Ir, 25166 alkylation, 3266 Chalcogenadistannirane, 39318 triselenocarbonate, 32:67 Chalcogen-bridged metal carbonyl com- , 3261 plexes reactions of 0sand Ru carbyne com- anionic clusters plexes with, 25191 hydro(so1vo) thermal preparations, reaction with organoplatinum halides, 4k250-252 27:128 stoichiometry influence on formation, sulfide ion 4k263, 265 metalloheterocycles, 3261 synthesis by reduction of Fe2S2(C0)6, nucleophilic attack, 3261 4k261-262 triatomic interchalcogens, M166-171 synthesis using polyanions, 4k254-259 Chalcogens, atom donors, reactions cationic clusters, 41:244-246, 248-250 alkyl complexes, 3251-52 neutral clusters allyltrimethylsilane, 3257 antiferromagnetic clusters, 4k305-306 aryl complexes, 3251-52 diazoalkane reactions, 4k283-284, 287, benzaldehydes, 3253 289, 292 carbene complexes, 3252-55 ironlmolybdenum clusters, 41:293, carbyne complexes, 32:55-57 295-300 dithiocarbamate, 32:56 metal fragment addition, 4k300-305 dithiocarboxylates, 3252 sulfurization reactions, 4k306-310 electrophilic attack, 3255 synthesis formaldehydes, 3252-53, 105 Chalcogens 62

heterocyclic carbene, 3258 charge-transfer substitution, 3370-71 heterocyclic selone, 3258 time-resolved spectra, 33:65-66, 69 heterocyclic thione, 3258 preparation, 3354-55 insertion, 3251 solvatochromism, 3360-62 , 3253 spectral characterization, 3354-56 molybdenum, 3255 visible absorption bands, 3356 nucleophilic attack, 3253 X-ray crystallographic studies, 3356-57 osmium, 3255 Charge-transfer substitution, 3370-71 selenocyanates, 3253 Charton's regression analysis, 36:136 telluroketone complex, 3255 C-H bond activation, and cyclometallated tetrasulfides, 3252 arene ruthenium complexes, thioacyl. 3256 29180-1 83 thiolate, 3257 CH2=SiMe(CH2SiMe3),42399 tungsten, 3255 Chelating agents, in alkali metal organics, Charge, germenes, M120 22185 Charge delocalization, in alkali metal organ- Chelating ligands, C,N -, see Organotin ics, 27:171-173 chemistry Charge distributions, of Os, Ir, and Ru car- Chemical effects, of nuclear transforma- bene complexes, 25124 tions, 1k208-249 Charge localization, in alkali metal eno- Chemically induced dynamic nuclear polar- lates, 22259 ization spectra Charge-transfer complexation, 34:149-152 of Grignard reagents, 16:144 Charge-transfer complexes, between arene- and Group I radical anions, 19275 metal compounds and a-acceptors, and organometallic radicals, 14347. 392 1168, 85 Chemical reduction Charge-transfer compounds, arganosilicon, in inert solvents, 2:128 see Organosilicon compounds, charge in proton-active solvents, 2128 transfer complexes theory, 21 16-1 17 Charge-transfer dimerization, 33:69-70 Chemical shift anisotropy, disilenes, stable, Charge-transfer disproportionation, 39242-243 3371-72 Chemical shifts Charge-transfer salts, carbonylmetallate '?C and 29Sifor silenes, 2514-15 anions in conversion factors, 34 bond angles and distances, 3357 reference standards, 34 characterization, 3354 theoretical calculation, 32 charge-transfer transitions, 3359-60 Chemical vapor deposition contact ion pair dissociation constants, advantages over other techniques, 40:217 3361 contaminant removal, 40:220, 323-324 1R spectra, 3358-60 difficulty with Group 2 elements, 40.217 isolation, 3354-56 film materials, 40:215-216 Mulliken charge-transfer theory, 3355- Group 2 compounds as precursors 56, 67 alkoxides, 40:315 photoexcitation, 3363-72 amides, 40,309 charge-transfer dimerization, 3x64, carboxylates, 40:324-325 68-70 cyclopentadienyl compounds, 40:311 charge-transfer disproportionation, P-diketonates 3371-72 fluorinated compounds, 40:315-316 charge-transfer mechanism, 3367-72 Lewis base adducts, 40:319-320 charge-transfer photochemistry, metal oxide film precursors, 3363-64 40:317-319 63 1-Chlorosilanamine

monodentate donors, 40320 stereochemistry of insertion reactions, polydentate donors, 40:320-324 18180-185 phosphides, 40:309 of carbon monoxide, 18182-183 poly(pyrazolyl)borates, 40.315 of sulfur dioxide, 18180-182 reactivity, 40:219-220, 328 tabulation, 18196-200 thiocarboxylates, 40:326-327 Chiral organo-transition metal complexes, transport, 40:220-223,328-329 13C NMR spectra, -290-293 volatility, 40:218-219, 223-224, diastereoisomer identification, 19:290 327-328 Chiral phosphines, 38179-181 precursor delivery Chloranil alkali metal compounds, struc- aerosol delivery, a222 tural data, 22245 apparatus, 40:220-221 Chlorides, aikyl, 28101 liquid delivery with flash evaporation, Chlorine-platinum bond, 38117-119 40:222-223 Chloroacetyl chloride, addition of metal car- supercritical fluid delivery, 40.223 bony1 anions, %28-29 steps in film formation, 40:216-217 Chloro(allyl)platinum, 37:229 Chemisorption, hydrogen, 267 Chlorodemethylation reactions, polysilanes, Chemotherapeutic index, 13:23 622 Chirality, 18:152 10-Chloro-5,10-dihydrophenarsazine,struc- and R,S-notation, 18194-195 ture, 4207 l-Chloro-2-[p-(dimethylamino)phenylltetra- Chiral metal complexes, 18 151-205 methyldisilane, reaction with lithium, absolute configuration, 18193-195 3836 notation, 18194-195 Chlorodisilane X-ray determination, 18193 reactions, 3811, 35-36 and asymmetric induction, 16:225 silyene-Lewis base complex synthesis, chiroptical properties, 18192-193 43:3 1 circular dichroism spectra, 18171, 2-Chloroethyldimethylamine,38164 192-194 Chloroform, reaction with germenes, 44:125 configurational stability, 18168-169 Chlorogermanes, 37:6 diastereoisomeric enantiomers, Chloromethane, formation, 38167 18189-192 (2-Chloromethy1ally)iron tricarbonyl chlo- separation, 18190-191 ride, 32239 ligand transformation, l8:169-172 Chlorome thylpolysilanes, 665 with inversion at metal, 18170-172 reactions, 666, 71, 73 with retention of metal configuration, Chloro(pentamethylcyclopentadieny1)meth- 18167- 170 ylaluminum, 26:242-243 optical induction, 18186-189 1-Chloro-2-phenyltetramethyldisilane, reac- asymmetric synthesis, 18186-188 tion with lithium, 3835-36 epimenzation equilibria, 18:188-189 Chloroplatinic acid optical purity, 18166-168 catalyst for hydrosilylation, 1k298, 300- optical resolution, 18153-165 302,13314-315 of diasteroisomers, 18:160-165 in hydrosilation catalysis, 12407, 409-427 of enantiomers, 18153-160 of acetylenes, 12443-445 optical rotatory dispersion spectra, with heterocyclic aminosilanes, 18192-194 12432-433 separation of diastereoisomers, nature of active species, 12411-415 18 165- 166 ring closure reactions, 17:416-419 square-pyramidal, metal-centered re- side reactions, 12419-427 arrangement, 18177-180 1-Chlorosilanamine, 39162 Chlorosilane 64

Chlorosilane, 326, 382-4, 10-11, 26 with acid halides, aldehydes, and ke- exchange reactions tones, 2242-43 hydrogen-chlorine, 19225 with alkyl halides, 2235-38, 40-41 methyl group-chlorine, 19:223 with Bronsted acids, 27:33 Chlorosulfonyl isocyanate, insertion into with Lewis acids, 2230-32 metal-carbon bonds, 1275-76 spectroscopic properties, 224-7, 23-25 l-Chloro-2,3,4,5-tetramethylarsole,39:330 structure, 229-14 1-Chloro-2,3,4,5-tetraphenylarsole, 39332 Chromium carbonyl compounds 0-Chlorovinyl ketones anion with cyclopentadienyl, 2191-202 complexes, 1032 dianions, 2182-184 substitution reactions, 1027 hydrides, 2200-202 syntheses, 1030-31 miscellaneous anions, 2188-190 Chlorovinyl-metal derivatives, 1012-13 monoanions, 2185-187 ((C5H5)MoFeTe2Br(CO)5], synthesis and Chromium carhonyl derivatives, 3196-213 structure, 41:248-249 diarsine complexes, halogenation, v5-C5H5ring, Group 4B carbonyl com- 3210-211 plexes containing, 25374-375 photochemical reactions, 3196, 207 Chromium Chromium, carbonyl diazene complexes in acyclic pentadienyl complexes, bond- activation energy, M83 ing parameters, 26140 bisdiazenes, 3480-81 hinuelear halo- and pseudohalo-decacar- diazene metathesis, 3493 bonyls diazetines, 3489-90 anions, 18:13-14 dimetallacycles, 3490-92 neutral compounds, 1816-17 electrochemical reduction, M92-93 IR bridge-terminal ligand exchange in ni- studies, 3483-84, 87 metal induced bond cleavages, 3498 trosyl complex, 16324 NMR studies, 34:82 compounds, ''C NMR spectra, 12:152, photochemistry, 3490 171, 173 preparation, 3480-81 cyclopentadienyl tricarbo derivatives thermal reactivity, 3490 with alkyl halides, 2:192-193 uv-vis spectrum, 3485 mercury, 2199-200 X-ray analysis, 3487-88 nitrosyls, 2201 Chromium carbonyls 7j"'diene CdIbOnylS, 26:298-299 cationic derivatives, 8133-159 mixed alkali metal compounds. 22214, substituted benzene a-complexes, 247, 249-250 8:227-231 organotin(I1) derivatives, 19143-146 Chromium carbonyls, substitution mecha- pentaearbonylhalides, 18:16-17 nisms anion, 1812-13 effect of hydroxide ion, 21:138-139 reaction with Lewis bases, 1817 hexacarbonyl derivatives, 2k115-118, reaction with liquid ammonia, 1832 121-122. 127-130 pentacarbonylhydride, 185 of amines, 2k127-130 substitution reactions of a-arene com- CO dissociation rate parameters, plexes, 10:366-370 2k117 Ziegler-Natta catalysts, 18106 ligand dissocation rate parameters, supported on silica, 18119-121 21:117 tris(acety1acetonate). 18125, 130 relative ligand lability, 2k117-118 Chromium, anionic hydride complexes with trans bis-ligands, 2k121 as catalyst, 2245 phenanthroline derivatives, 21:143 reactions, 2228-29 stereoselectivity, 2k140-141 Chromium complexes

tetracarbonyl norbornadiene complex, reactions with conjugated dienes, 2k132-134 26298-299,316 I3CO substitution, 2k133 indium, 39:57 Chromium, carbyne complexes isocyanides, 22251-252 bonding, 27:52-53 arenes, 22218 reactions carbonyls, 22225-227, 229-230 carbyne cleavage, 2297-98 electrochemistry, 22255 carbyne coupling, 2283-84 compounds, 22221-222 with nucleophiles, 27:70-75 pentacarbonyls, 22214, 217-218, 225 spectroscopic properties, 2256 lithium derivatives structure, 2253-55 with chloride bridges, 24440 synthesis, 2257-59, 68 methyl complex, 24395-396 Chromium complexes, 3953 with 0-bridging ligands, M43 alkylchromium(III), 38156-160 main group arene, 1351, 55-56,61-77,80-89 antimony and bismuth, 3k130-137 as hydrogenation catalysts, 12336 germanium, tin, and lead, 3k108-113 on polymer supports, 12365 tellurium, 3k155-157 arenetricarbonyl derivatives supported on mixed-metal germanium, 26:264 polystyrene, 15201 nitrosyls bimetallic, 32266-268, 273-274, 289, carbonyl anion, 2447 291-294,297-298,300-301,306,308 carbonyl cyclopentadienyl, N43, 59 of boranes, 2k63-64 iron clusters, 2448, 51 butadiene oxapropadienylidene, 22114 "C NMR spectrum, 19276 pentacarbonyl(2-) anion, 3k19, 21 carbene, 1k52 perfluorobenzene, 3k199 carbonyl diazirine, 34:81, 86 phenylethynyl, 38122, 135-136 chiral arene, 18196 photochemistry optical resolution, 18157-158 and p-lactam synthesis, 24333-334 C,O-bonded carbonyls, 23233-236 cyclic carbenes, 24329-331 n-cycloheptatriene-8-cyclopentadienyl, cyclopentadienyl alkyls, 24:280-287 1369 tetraalkyls, 24275-276 cyclopentadienyls and bis(trimethylsily1)- propadienylidenes, 2283-85, 101, diazene, 23:184-188 110-111 cyclopentadienyltricarbonyl reactions, 2287 migratory insertion reactions, 26189 $-SiH, 30172-173 of 1,4-diaza-l,3-butadienes of substituted cyclopentadienyls, 21:9, 36 as catalyst, 2k233 synthesis via metal atoms, 1590-92 with chelated ligand, 2k170, 172-174 and cyclooctadienes, 1566-67 with monodentate ligand, 2k165 and polyenes, 1577, 91 -92 radical anion, 2k217 tetracarbonyl(4-) anion, 3k39-43 dicarbonylbis( v4-diene) thallium, 3957 dynamic behavior, 26:314-315 tricarbony1-~4*-bi~y~1o[4.4.1]undeca-2,4,8- stereochemistry, 26311-313 trienechromium, 26329-330 v4-diene tetracarbonyl tricarbonyl-~h-1,3,5-cycloheptatriene stereochemistry, 26:300-302 reactions with conjugated dienes, electron-deficient diene, 26:315-325 -325-335 synthesis, 26315-316 trimetallic, 32269, 298-300 formyl, 20:6 trimethylenemethane heterobimetallic fulvalenyl, 303 synthesis, 22281 hexacarbonyl, 3k15, 21 vinylidenes, 2288 Chromium complexes 66

pentacarbonyls, 2263, 66, 95-96, Chronopotentiometry of substituted ferro- 104-105 cenes, 10100 ylide, 20153 [I(~-CH~TC)F~Z(CO)~IZI~-T~CHZT~-~]I, Chromium complexes, electron-transfer re- synthesis and structure, 41:287, 291 actions Cinnamaldehyde, reaction with silenes, arenes, 2491-93 39125 arenetricarbonyls, 2364-65, 78-79 Circular dichroism oxidation vs. substitution, 2364 and chiral metal complexes, 18171, aryls, 2334-35 192- 194 bis(arenes), 23:67-68 vinylketenes, 44:348-349 bis(cyclopentadieny1) compound, 2368 Cis-M(CbX,),(OC4H8)z, synthesis of, bridged bimetallics, 24100-101 28243-254 carbonyl derivatives Citric acid, in spirocyclic h5Si-silicates, acyls, 235 a241 carbenes, 235, 8-9 CsK cyanide, 239 reactions, 28:99-103 halides, 23:18 C-C bond formation, 28105-106 of N-donors, 2312-13 C-C bond scission, 28:105-106 redox potentials, 236-7 synthesis of Ni(0) compounds, carbony lphosphines 28:106-107 ferrocenyl derivatives, 2314-15 Classification, triosmium clusters, 264-39 isomerization, 23:15-16 CIz(CO)(PPhzMe)zWP(C6H,BU3),structure cycloheptatricnes, 2365 and bonding factors, 4219 cycloheptatrienyl, 2365 closo-Carboranes cyclooctatetraene cyclopentadienyl, 2493 electron counting, X31 cyclopentadienyls, 23:47 geometrical systematics and electron pair isocyanides, 236-7,9-11 relationships, N22-29 palladium and platinum clustcrs, nomcnclaturc, N32 24111-112 structures, 362-7. 12-15 sandwich compounds, 2367-69 thermal stability and fuel value, N17-18 Chromium-graphite, 28:129-130 Cluster catalysis Chromium, substituted di~arbonyl(17J'~~- anionic species, 32132-137 diene) complexes dinuclear ruthenium complexes, 32137 diene rotation, 26322 mechanistic studies, 32137-139 dynamic behavior, 26:319-323 mixed ruthenium-rhodium complexes, hydride shifts, 26322-323 32131 hydrogen-bridge exchange, 26319, mononuclear ruthenium complexes, 321 -322 32130, 132 ligand exchange, 26321-322 neutral species, 32129-132 molecular structure, 2&318-319 polynuclear ruthenium complexes, 32130, stereochemistry, 26:316-317 132, 137, 139 synthesis, 26:316 [Ru,(CO),,;], catalytic activity, 32129- Chromium, substituted ~~-dienecarbonyl 132, 134-135 complexes Cluster complexes carbonyl scrambling, 26:304-305 and boranes, 2k58-59 diene ligand rotation, 26:305, 308-310 heteronietallic, see Mixed-metal clusters isomerization, 26305-307 Cluster compounds ligand exchange, 26:310-311 acetylide-bridged, 32122 structure, 26303 allenyl, 3276 synthesis, 26:300 bisalkylidyne, 37:67 67 Cobalt

expansion reactions, 32116 bis(cyc1ooctadiene) anion, 19113 giant, 3236 ligand displacement, 19:116 metalloallyl, 3272, 77 reaction with methanol, 19116 of osmium, see Triosmium clusters structure of lithium derivative, polyhedranes with silicon, germanium, 19115-116 and tin, 321-36 corrinoids, 1k338, 384-386 theoretical studies, 1540-45 structures, 1k341, 345-346 transition metal allenyl complexes, synthesis, 1k363-364 3257-124 dicarbonylcyclopentadienyl Cluster formation, by tungsten alkoxides, nitrosylation, 20173 22352-353 reaction with diazoalkanes, 20169-171 Clusters dicyclopentadienyl allene bridged, 3287 reaction with Lewis bases, 19156 iron and ruthenium, main group, ring cleavage reactions, 19112-114 3k101-106 high nuclearity carbonyl clusters, 14287- with more than two different metals, 288, 325-327 3k376-383 carbide-derivatives, 14327 bridging alkylidyne ligand, 3k380-383 IR spectra, 14326-327 tri- and tetra-nuclear, 31:377-379 reactions, 14:325-327 platinum heteronuclear, 3k301-391 structural data, 14288 CNDO calculations synthesis, 14325-327 on bridged electron-deficient main group hydrides, 1k351 compounds, 15237 hydrocarbonyl, reactions aluminum, 13250 acylcobalt tetracarbonyls, 4255 on Group IVB radical anions, 15304-305 acyl halides, 4245 and mechanism of Wacker process, epoxides, 4245 16253-254 olefins, 4244 Coal, and Fischer-Tropsch reaction, isocyanide derivatives, 1k63 1261-65 mixed alkali metal compounds, 22209- Cobalamins, photochemical reactions, 211, 217,246-252, 256 1k403 s-complexes Cobaloximes, 13:25 order of reactivity toward nucleophiles, catalytic reduction, 1k437 1350 insertion of oxygen, 1k431 polymer-supported carbonyls as hydrofor- isocyanide derivatives, 1k63 mylation catalysts, 15218-222 as models for vitamin BIZcoenzyme, porphyrins, organic derivatives, 1k364 16276-278 substitutian of acetylene complexes, organo derivatives, 1k367-374 10:354 Cobaloxime system, 2161, 203 synthesis of complexes via metal atoms, Cobalt 1597-98 y-alkanediyls, 20239-240 tetrakis(ethy1ene) anion, 19112-113 y-alkylidenes, 20250-251 ligand displacement, 19116 alkylidyne nonacarbonyl clusters, structure, 19115 1497-144 in triosmium clusters, a78-80 anionic hydride complexes as catalysts, Cobaltacyclobutenes, in vinylketene synthe- 2244 sis, 44301-302 spectroscopic properties, 275, 23 Cobalt, alkyne complexes structure, 229-10 dinuclear complexes bis(butadiene) anion, 19116-117 carbonyl ligand substitution, 4k82-84, zinc derivative, 19117 86,88-91, 93 Cobalt 68

chirality, 41:90-91, 98-100 with eleven metal atoms, 22:37 crystal structures, 4k76-77, 82-83, with thirteen metal atoms, 2237-38 89-90 effective radius of carbide, 2250 dicationic species, synthesis, hexanuclear pentadecacarbonyl dianion, 41: 102- 103 2233, 201 IR spectroscopy, 41:82 condensation with cobalt carbonyl, mixed-metal complexes, 4k72-74 2236 molecular orbital calculations, 41:79, ferric ion oxidation, 22:34-35 81, 90 13C NMR spcctrum, 2247 monocationic species hexanuclear tetradecacarbonyl monoa- crystal structures, 4k94-96 nion, 2235 IR spectroscopy, 4k95 structure, 2236 nuclear magnetic resonance, tropylium ion oxidation, 2235 4k95-96 octanuclear octadecacarbonyl dianion, reactivity, 41:94. 98-102 2236-37,201 stcrcoselective synthesis applications, sulfur derivatives, 2239-40 4k98-100 Cobalt-carbon (+ bonds synthesis, 4k93-94 cleavage, 1k401-433 NMR, 41232, 84 effect of ligands, 1k419-421 radical species, 41:103-105 climination reactions, 1k408-412. synthesis, 41:69-76 427-431 organic synthesis applications, 4k94, 98- homolytic fission, 1k405 102, 117-119 insertion reactions, 1k427-431 pentaheteronuclear clusters, 41:115 intramolecular displacements, 1k407-408 tetranuclear complexcs oxidation, 11:432 geometries, 41~110-112 photochemical reactions, 11:403-405 synthesis, 4k112-115 reduction, 1k432 trinuclear clusters solvent effects, 11:406 heteronuclear compounds, 4k108-110 thermolysis, 1k405 synthesis, 4k105-108 transfer reactions, 1k421-427 Cobalt, binuclear p-methylene complexes Cobalt carbonyl, 12324-325, 337-338 via p-alkoxycarbonyl carbenes, 20171 acetylene complexes as polymerization in- carbonylcyclopentadienyls,20169-171, hibitors, 6:165 182,249 acyl- and alkyl derivatives, 4:243-266 via acetaldehyde enolate, 20191 amine complexes, 8:4 via carbene addition reaction, 20245 cationic derivatives, 8152-155 from diazoalkanes, 20168-170 anion derivatives via metallacycles, 20169-170 acrylyl derivatives, 2243 thermal stability, 20216 alkylcobalt tetracarbonyl derivatives, germylene analogue, fluxionality, 2238 20235-237 ally1 compounds, 2242-243 y-lactone derivatives, 20163-164, 250 metal derivatives, 2246-247 C-0 cleavage, 20163 nitrosyl derivatives, 2248-249 reaction with acetylenes, 20:163-164, perfluoro derivatives, 2238-239 222, 247 phosphine derivatives, 2:237-241 heptacarbonyls, 201 68 preparation with Lewis bases, 2235 Cobalt carbidocarbonyl clusters, 2233-43, reactions with triphenylphosphine, 2:2 54 transition metal derivatives, 2248 carbide carbon chemical shift, 2247 trinuclear dcrivatives, 2243-246 dicarbides, 2237-38 carbonylation reactions, 6158-163 69 Cobalt complexes

carboxylation, 6119-165 borabenzene, 13112,174, 253 hydrogenation, 6147 of boranes, 2k63-66,68-70,82,102-103 reactions, 6157 isomerism, 2k94-95 reactions, general, 6121 multinuclear species, 2k98-102,104 catalysis of propene hydroformylation, carbamoyls, 1825-27 a200 of carbon dioxide, 22132-133 complexes with silanes, 6152 carbonyl cyclization of acetylenes, 6163 clusters, reaction with alkynes, 22185 derivatives, 3237-243 hydride, 30196-197 halides, 3241-242 nitrosyl, 30195-196 nitrosyls, 3240-241 carbonyl bridged ytterbium derivative, organic derivatives, 3242-243 M166 phosphine complexes, 3237-243 carbyne 3:239-240 sulfur complexes, carbyne coupling, 2284 6278 mass spectrum, with nucleophiles, 2E74 19190-197 in phase-transfer catalysis, chiral cyclopentadienyls, 18185-186,199 reaction with alkynes, 12.323-371 cluster, 30226-228 Cobalt carbonyl halides, phosphine deriva- cyclobutadiene, 15122-123 tives, 814 cyclopentadienyl, 19113-114 Cobalt carbonyl hydride, 87 bis(ethylene), 19:114 olefin isornerization, 6153 diene, 19:113-114 Cobalt chloride, role as catalyst in Grignard 19114-115 reactions, 12:283-284 reaction with alkali metals, of 1,4-diaza-1,3-butadienes Cobalt complex catalysts 2k168-169, codimerization of ethylene and butadi- with chelated ligand, 181-182 ene, 17:309-315 ethylene glycol synthesis, 1280 mixed binuclear carbonyls with manga- hydroformylation, 123-53 nese, 2k162-163,177, 195-198, hydrogenation 205,208-209 via dinitrogen complex, 12331 dicarbonyl cyclopentadienyls, 2k9-10 with pentacyano anion, 12324, associative substitution mechanism, 334-335 2k124 hydrosilation, 12431-432 with halogen substituents, 2k26-28 of conjugated dienes, 12442 polymer-bound catalyst, 21:48-51 formation of silacyclopentane, 12416 reactions at ring, 2k10 of hex-1-ene, 12428 vinyls, 2k41-43 and olefin isomerization, 12428-429 edge-bridged Z-C,O-bonded carbonyls Ziegler-type catalysts, 12430 aluminum derivatives, 23251 Cobalt complexes with lanthanide acceptors, 23251-252 acyclic pentadienylrnetal, 26137,141-142 lithium cluster, 23249 alkyl, 38108 on silica, 23256 alkylcobalt (111) , 381 60-162 face-bridged Z-C,O-bonded carbonyls alkylidyne carbaborane, 3k69 acyl, 23265 alkynyl, 38108, 111 with alkali metals, 23258-260 arene, 1366,79, 111-113 Group I11 derivatives, 23260-262 bimetallic, 32229,234, 257-258,270, 272, with protons, 23257-259 287 silicon derivatives, 23:264 binuclear n-C,O-bonded carbonyls, with transition metal acceptors, 23267 23270-271 of uranium cyclopentadienyl, 23267 bis(discarbonyl)fulvalene, 2k28 heterocarborane, W139,144 Cobalt complexes 70

heteropolynuclear II-C.0-bonded clus- carbonyls, 23104,115 ters, 23276-278 cyclopentadienyl compounds, 23106, p-hexafluorocyclooctatrieneyne, 109. 112,123-124 3k255-260 nitrosyls, 23126 with hydrocarbons, mass spectra, sandwich, 32304-305 8272-276 silyl, 1k257-258 hydroformylation, 34254-255 in hydrosilylation reactions, 1k306-307 indium, 3956 polynuclear derivatives, 1k289-290 isocyanides, 22264 terminal I;-C,O-bonded carbonyls clusters, 22229 with alkali metals, 23230 cyclopcntadicnyls, 2221 9,231 with magnesium ions, 23235-236 electrochemistry, 22:255 with ytterbium complex, 23240-241 homoleptic species, 22222,248, 252, tetracarbonyl radical, 2k143 259 tricarbonylmetallate(3-) anion, 3k31-36 main group tricarbonyl trianion, 189 antimony and bismuth, 31:148-154 tricobaltnonacarbanyl cation derivatives, gallium, indium, and thallium, 18265 3k106-107 vinylidenes germanium, tin, and lead, 3k122-126 binuclear lactone hexacarbonyls, 2277, tellurium, 31:167-168, 172-173,175 103,109 mixed metal B sandwich clusters. 22116-117 with thallium, 26256 Cobalt complexes, electron-transfer reac- with tin, 26276 tions nitrido clusters, B63-64, 69,71, 74,76 p-acetylene hexacarbonyl derivatives, with ruthenium, 2465 a10% 1 10 nitrosyls p-alkylidynes, B112-113, 117-118, 124 carbonyl, 24.43 allyl, 2337 clusters, B46,48, 50-53-24:64 carbonyl, 2328-29 octacarbonyl, reactions Group IVB derivatives, 2328-29 with ammonia, 1821 carbonyl-bridged q4 diene derivatives, with Lewis bases, 1845-46 a110 octafluorocycloocta-l,3,5,7-tetraenederiv- carborane triple deckers, M96 ative, 3k217-239 cobaltocenes, 2375-76 pentamethylcyclopentadienyl, cubanes, 241 19 3k225-229 cyclooctatetraene cyclopentadienyl, B97 perfluorobicyclo[3.30]octadienediyl, cyclopentadienyls 31:221-225,230-233 arenes, 2376 organic derivatives, 1k331-441 carbonyl oxidative substitution, organolithium derivatives 2357-58 allenyl cyclooctadiene, 24404-405,407 diene reductive isomerization, 2360- cyclooctadiene, 24:399-400 62,78 ethylene tris (phosphine) complex, dimeric cyclopentadienyls, 24.104, 106- B402-403 108, 110, 123 perfluorocyclopentadienyl, 3k25.5-260 face capped trinuclear derivatives, 24117 phenylethynyl, 38125-126,137 ferrocenylcyclobutadiene derivatives, phosphaalkyne, 30213-215 2491 reactions with bis(trimethylsilyl)diazene, fulvalenes, a94 231 85 Group V donor bridged carbonyls, 24100 redistribution reactions halogen-bridged cyclopentadienyls, alkyls, 23123-124 24123 71 Cobalt

hexanuclear carbonyl cluster, 24:120 reactions with organic halogen com- isocyanides, 2332 pounds, 1k352-356 mediated by carbonyl ligands, 23296 acyl halides, 11:352 nitrosyls, 2332-33 alkenyl halides, 1k355 n-bridged iron carbonyls cluster, alkyl halides, 1k353-355 M121-124 alkynyl halides, 11:355 phosphines, 2329-32 aryl halides, 1k356 dimerization, 2329-30 epoxides, 1k352 hydrides, 2331 Schiff base complexes, 1k375-381 trinuclear carbonyl, 23295-296 Cobalt(I1) cyanide complexes, as alkene hy- trinuclear cyclopentadienyls, a119 drogenation catalysts, 38171-172 Cobalt complexes, organic derivatives, see Cobalt(I1) complexes, 11:3.58-360, 389-390 also Organo-cobalt complexes conversion to organocobalt(II1) com- cis and trans effects, 1k349 pounds, 1k358-360 isomerism, 1k348 electron transfer reactions, 11:389 ligand structure, 1k347 radical reactions, 1k389 nomenclature, 1k336-341 reactions, 1k358-360 reactions, 11:335, 360-361 Cobalt(II1)-catalyzed oxidation synthesis, 1k350-383 of alkanes, 15182-184 from cobalt hydrides, 11:351-358 of cyclohexane, 15182-183 from cobalt(I1) compounds, 1k358 Cobalt(II1) complexes, 1k360-361, 390-394 valence states, 1k341-342 ligand effects, 1k391-393 nucleophiIic attack, 11:390 Cobalt complexes, photochemistry Cobalt compounds, see Organotin chem- benzyl pentacyanide trianion, 24300-301 istry with oxygen, 24301 "Cobalt y-irradiation, of metal complexes trinuclear nonacarbonyl alkylidynes, chromium, molybdenum, and tungsten, 24342-343 2318 and alkene isomerization, 24:343 cobalt, 2328, 57 under CO, 24342-343 iron, 2378 electronic spectrum, 24:343 manganese, 2318, 20, 78 with water, 24342-343 titanium, 2343 vitamin BIZmodels, 24302-304, 311 Cobalt-graphite compounds, 2894 alkyl cobalamins, 24:303-304, 309 Cobalticinium salts, NMR spectra, 10:88 bipyridyl derivatives, 24310-311 Cobalt, mixed-metal clusters, 18210-212, cobaloximes, 24305-309,311 215-225 ESR studies, 24304-305 iron carbonylhydride flash photolysis, M308 as norbornadiene dimerization catalyst, primary photoprocess, 24:304-305 18256 Cobalt(1) complexes stereochemical nonrigidity, 18260-261 addition reactions, 1k351-358 substitution, 18250-251 acetylenes, 1k352, 357 ironruthenium carbonyl anions, 18253 olefins, 1k3.52, 356-357 platinum carbonyls, 18236-237 addition to unsaturated compounds, rhodium carbonyls, 18223-225 11:388-389 adsorption onto alumina and silica, alkylation, 11:353-358 18257 kinetics, 11:354 as hydrogenation catalysts, 18256 carbonylation, 1k131-133 stereochemical nonrigidity, 18259-260 with macrocyclic ligands, 1k384-396 synthesis, 18238 nucleophilic attack, 11:386-388 ruthenium carbonylhydride, 18221-222 Cobalt 72

stereochemical nonrigidity, 18259-260 electrorcduction, 34:123 Cobaltocene nickel complexes, M121-123 absorption spectroscopy and substituent nucleophilic substitution, 34122 effect, 40:133-135 olefins, conversion to, 34121 bis(dimethylaminomethyl), 2k31 palladium complexes, 34122-123 bis(diphenylphosphide), 21:34, 36 platinum complexes, 34:123 cyclopentadienyl ring orientation, allylic 40:118-119 alkoxide generation, 34118-119 1,1'-diacetyl, 21% cobalt complexes, 34124 I .l'-dicarbomethoxy, 21:R ketone production, 34119 molecular mechanics calculations, nucleophilicity, 34118 40:135-136 palladium complexes, 34118, 126 molecular orbital calculations, 40:132-133 platinum complexes, 34:118 oxidation, 2384 product isolation, 34118 structural distortions induced by bulky reactions, 34124-126 suhstituents, 40138 rhodium complexes, 34:124-126 synthesis, 2378-380 ruthenium complexes, 34124 Cobalt-platinum cluster SN2' reaction, 34125-126 crystallographically characterized, 3k337 allylic carboxylates high nuclearity ally1 acetate, 34:115-116 carbido species, 3k365-366 allyl formate, 34116-1 17 trigonal bipyramidal skeleton, 3k365 anti elimination, 34:114 synthesis, 31:303-305 carboxylate anion exchange, N117 tri-nuclear and tetra-nuclear catalytic processes, 34116 electrochemical study, 31:364-365 molybdenum complexes, U117, 119 phosphido-hridged species, 3k364 nickel complexes, 34116 preparation, 3k363-364 palladium complexes, 34114-117 Cobalt tetracarbonyl anion and derivatives, reductive cleavage, 34117 2234-240 reductive elimination, 34115 alkylcobalt tetracarbonyl derivatives, stereochemical studies, 34114-1 15 2:238 syn elimination, 34:114 hydride, 2236-238 allylic ethers perfluoroalkyl derivatives, 2238-239 alkenyloxiranes, 34120-121 preparation, 2234 allyl phenyl chalcogcnides, 34119 triphcnylphosphine derivatives. 2239-240 catalytic processes, 34120 Cobinamides, see also Organocobalt eom- cobalt complexes, M126-127 plexes deuterated isomers, 34128 isocyanide derivatives, 11:63 diallyl ether, 34120, 126 C - 0 bond cleavage insertion-elimination, 34126-128 acid anhydrides, 34134-136 nickel complexes, M120 iridium complexes, 34A34 palladium complexes, 34119-121 nickel complexes, 34134-135 platinum complexes, 34:127 palladium complexes, 34:135 reaction, 34:119-120 alcohols, 34138-139 rhodium complexes, 34128 alkenyl carboxylatcs silicon complexes, 34:127 olcfinic insertion, 34128-129 SN2' reaction, 34:128 ruthenium complexes, 34129 stereospecific reduction, 34:121 allylic alcohols cyclic ethers, 34136-138 amination, 34123 copper complexes, 34137 catalytic dismutation, 34121-1 22 iridium complexes, 341 36 73 Codirnerization

platinum complexes, 34136 Co2(C0)6(m-SiGe2)2,fluxional behavior, rhodium complexes, 34137 42275 titanium complexes, 34137 Co2(CO)6(m-SiMez)2,synthesis, 42244 tungsten complexes, 34138 Cocondensation esters 0s with benzene, 29237 carboxylic, 34130-132 0s with benzene-2-methylpropane, Heck-type arylation, 34134 29238 iridium complexes, 34132 0swith mesitylene, 29:237 lactones, 34132 Ru with 1,3-yclohexadiene, 29237 nickel complexes, 34:130-132 [Co6(CO)16P]-,structure and bonding fac- palladium complexes, XI32 tors, 4239 sulfonates, 34132-134 CO~(CO)~P~~(CO)~,synthesis, 4290 C=O bond cleavage Co2(C0)4(PPh3)2As2,synthesis, 42:115 aldehydes, 34141 Co4(C0),2Sb4, synthesis, 42113 esters, 34:143 [CoCpFe2(C0)6(p3-Se)2],synthesis and Grubb’s reagent, 34141 structure, 4k303-305 ketenes, 34141 [COC~F~~(CO),(~,-SS~)~],synthesis and ketones, 34141-142 structure, 41:303-306 ruthenium complexes, 34141 [((CO)SC~),AS(C~)X]-,synthesis, 42101 Tebbe’s reagent, 34140-141 Cocyclization catalyzed by palladium com- titanium complexes, 34140-141 plexes, 12176-178 tungsten complexes, 34:141-142 of butadiene Wittig reaction, 34140 with aldehydes, 12176 Co(C0); with arylisocyanates, 17:178 with ketones, 12176-177 bond angles and distances, 3357 with Schiff bases, 17:178 charge transfer, photoexcitation of, of isoprene, with arylisocyanates, 12178 3363-64 Codimeriza tion charge-transfer photochemistry, mecha- dienes with acrylic esters, 1569 nism of, 3367-72 ethylene and butadiene, 17:269-318 dimerization, 3364, 68-70 catalyzed by cobalt and iron com- disproportionation, 3371-72 plexes, 12309-315 substitution, 3370-71 alkylaluminum cocatalysts, charge-transfer transitions, 3360 12310-311 contact ion pair dissociation constants, comparison with other metals, 12315 3361 effect of phosphine ligands, IR spectra, 3359 12310-313 preparation, 33:54-55 formation of cis-l,4-hexadiene, solvatochromism, 3360-61 12309 space filling model, 3358 mechanism, 12313-315 spectra, visible absorption bands, nature of active catalyst, 12311-313 3355-56 selectivity, 12314 time resolved spectra, 33:65-67 catalyzed by nickel complexes, 12205, X-ray crystallography, 3357-58 208, 291-308 [CO~(CO)~AS]?,synthesis, 4286 1:2 adduct formation, 17:291 Col(CO)qAsCr(CO)s, synthesis, 4279 alkylaluminum cocatalysts, 12291- CO~(CO),~B~~,synthesis, 42110 292,296-298 [CO?(CO),E]~,synthesis, 4289-90 butadiene polymerization, 12297 Cod(CO),( F,PN( Me)PF2I4(PPh), structure catalyst structure and selectivity, and bonding factors, 4230 12307-308 Codirnerization 74

cocatalysts structure vs. activity, stereoselectivity and ligand effects, 12206-298 12285-287 comparison with rhodium, 12291 ethylene and styrene, 12137 n-crotyl intermediates, 12292-293 [(CO),F~ZP~(PP~,)Z(~-S~C(P~)C(H))I,syn- 1,4-hexadiene isomerization, 12297 thesis and structure, 4k276, 281 hydrides, 12205,208 [(CO)6Fe2(p-SeCHZTe)],synthesis and inhibition by bidentate phosphines, structure, 4k292 12295-296 [((CO)~Fez(p-Sez)2C(Ph)--C(H)]],synthesis isomer distribution, 12308 and structure, 4k275, 277 mechanism, 12293 I(C~)SF~~(~-~~Z),C(P~)C(H)(~-~PP~)I,syn- nature of active catalyst, 12291 thesis and structure, 4k276, 280 phosphine ligand effects, 12295-297, [( CO),Fe,(p-SeC(Ph)C(H)Se)], synthesis 300-302 and structure, 4k275, 277 selectivity-controlling reactions, [((CO)3Fe(p-SeTe)),], synthesis and struc- 12304-305 ture, 4k292-293 stereoselectivity, 17:300-307 [(CO),Fe2STe(C(H)CH3),],synthesis and catalyzed by palladium complexes, structure, 4k283-284,290 trans-1.4-hcxadiene formation. [( CO),Fe2(,a-TeCH2Te)], synthesis and 12315-316 structure, 4k287, 290 catalyzed by rhodium complexes, [(CO)6Fe2(p-TeMe)2],synthesis and struc- 12271-291 ture, 4k287, 291 1,2-addition to butadiene, COLOC, 28440-441 12277-278 Color Test 1, 7:6 butadiene polymerization, 12271- [(CO),M(E=C(C,H,R-p)H)], synthesis, 272,276 43156 catalyst nature vs. isomer distribu- [(CO)sM(~'-S=CMe,)], synthesis, 43:146 tion, 12270-271 [(C0)4Mn(PPh2)LC-S6-C(PPh2)2) catalyst reactivation, 12278-283 M-n(CO),], synthesis and structure, use of crotyl complex, 12283-290 4k306-307 a-crotyl intermediates, 12272-273, [(CO),MP7]-, synthesis, 4287 275-277, 281 Competition kinetic method, Group 14 hy- effects of solvating ligands, drides, M72-73 12283-290 (CO,)M(PM(CO),),, synthesis, 42103 isomer distribution, 17:288-290 Comproportionation reactions, of molybde- isomerization of 1,4-hexadiene, num and tungsten alkoxides, 2R328 12277 Computers, in organometallic chemistry mechanism of 1,Chexadiene forma- and catalysis, 26:165-216 tion, 12272-275 Condensation reactions nature of active species, 12272-274 ferrocene-organosilane polymers by, organic halides as activators, 32136-137 17:279-283 poly(ferocenylphosphines)by, 37:153-154 rate dependence on butadiene con- Cone angle, ligands, and racemization of centration, 17:274 chiral complexes, 18:175-176 reaction kinetics, 17:274-275 Configuration interaction, 2136 reaction rate and ligand effects, Conformation angle, in bis(pentadieny1)- 12284-287 metal complexes, 26:139-140 use of rhodium(1) species, Conformers, of pentadienyllithium and pen- 12273-274 tadienylpotassium complexes, 26:128 selectivity, 12275-277 Conjugation phenomena, 10:20 75

Contact ion pairs, electron-transfer equi- carbenoids, l2309 libria catalysis of a-additions to isocyanides, establishment, 3387 1k47 P+TpM(CO);, electron transfer, equilib- corrosion in seawater, 3871-74 rium constants for, 3395 mixed-metal clusters, 18220, 225, 239 TpM(CO)<, evaluation of, 3393-96 organic chemistry, l2215-313 TpM( CO)

hydride, 12253 correlation with trans-effect, isocyanide complexes, as catalysts, 12.159-160 U307-310 metal acetylene complexes, Coppcr(I1) catalysts, 38:171 12:160-161 Copper(I1) chloride metal olefin complexes, U160 use in olefin oxidation in acetic acid, indirect coupling constants, 12161-162 13395-397 metal carbonyl derivatives, U161 in Wackcr process, 13379, 384-385 numerical data, 12195-199 Copper isocyanide complexes, 1k48-49, 80 for silenes, 2514-15 Copper oxide-isocyanide mixtures, as cata- spin-spin, 33 lysts, 11:48-49 Coupling reactions CO~(PP~,),(FL,-AS)~(~~,~'+W,structure C-C, interligand, of metalla derivatives and bonding factors, 4254-55 of 0-diketones, 2560-70 CO~(PP~?)~(F~-PP~)~,synthesis, 4281 computer representation, 26:178, 184- [Co(PR,)( q'-S =CPh,)( q5-C5H5)],synthesis, 185, 190-191 43146 affording four-membered metalla- [ ( CO),Re][(C0)3Re]2[As8Me7],structure cycles, 26:187 and bonding factors, 4275 feasibility matrix, 26:185 Corrinoids, 1k338, 384-386 of p-ligands, 26:190-191 organo derivatives, 1k384-386 of n-allylic nickel halides, 844 photochemical reduction, 1k403 with nitriles, 836 reduced forms, 1k385 with organic halides, 836 addition to acetylcncs, 1k386 in transition metal carbynes, 217:83-85 unsaturated compounds, 11:385 Covalent compounds, a89 reactions with alkyl halides, 11:385 ((CO),,W)2((CO)5W)SbR,synthesis, 42101 Corrosion, in seawater, alkyl halides and, [(CO),W(~'-Se=CHC(Ph)=C(Ph) OEt)], 3&71-74 synthesis, 43156 Cotton-Kraihanzel method (C0)3WP5SiMe3,synthesis, 42100 for calculation of carbonyl stretching [(CO),W(Tc=C(Ph)=C(Ph)Oet]], synthesis, force constants, 1510 43156 intensity measurements, 10218 [CpZBNb]2As~.structure and bonding fac- in metal carbonyl IR spcctra, 10200, tors, 4275 213-214 (Cp'B)RhP4(r(CO)5],,synthesis, 4292 Coupling, mechanism of nickel-catalyzed re- [(CP'~)~T~]~P~,structure and bonding fac- action, 882-83 tors, 4268 of ally1 groups, 830-39 [Cp(CO)zCr]5Plo,structurc and bonding fac- Coupling constants tors, 4274 in "C NMR spectroscopy, U155-165 [(Cp(C0)2Fe)2EX2]+,synthesis, 42110 determination of sign, 12137 [(Cp(C0)2FeJ3SbC1]2[FeC14],synthesis, direct carbon-fluorine, 12:165, 206 4279 direct carbon-hydrogen, 12:162-165, c~(Co)~MbiMe~,synthesis, 4281 200-205 [Cp(CO)2Mn]Z-,structure and bonding fac- carboranes, U164 tors, 4214, 17 cyclopentadienyls, 12163-165, 202 [Cp(C0)3Mo]2BiR,structure and bonding platinum phosphine complexes, factors, 426-7 12163 [Cp*Co]2[Mo(CO)3]As6,synthesis, 4290 silicon complexes, U162-163, 203 Cp2(C0)4MoR, structure and bonding fac- direct metal-carbon, U1.56-161 tors, 4245 correlation with bond strengths, (Cp*Co),(P,),, synthesis, 4288 12159 CpCr(C0)2H, synthesis, 4288 77 Cp,M(R)+ complexes

[CpCrI2PS,structure and bonding factors, Lewis acid-base chemistry, 32349-352 4259 ligand C-H activation, 32362-366 Cp2Fe2(C0)2(p-CO)(p-GeMe2),isomeriza- olefin reactions, 32366-369 tion, 42279 productive C-H activiation, catalytic, Cp*2Fe2(CO),(p-CO)(pGep-TolH),isom- 32~378-381 erization, 42283 reactivity, 32349-369 Cp2FeZ(C0)2(p-CO)(p-Get-BuX),synthe- structures, 32:337-348 sis, 42262 Ziegler-Natta olefin polymerization, his- Cp*,Fe2(CO)z(p-CO)(p-Sip-TolH),isomer- torical interest, 32327-329 ization, 42282-283 Ziegler-Natta systems, cationic complexes CP,F~,(CO)Z(~-C~)(~-S~R~) in, 32370-374 absorbance spectroscopy, 42273,285 Zr-P-CH2-Si interactions, 32343-346 NMR, 42273 Zr-R bond hydrogenolysis, 32360-362 CpZFeZ(CO)Z(p-CO)(p-SiRX),isomeriza- [(C4PMe2Ph)4Na2(DME)2],synthesis and tion, 42280-282 structure, 43301 CpFe(CO),SiH2t-Bu, synthesis, 42236 [CpMn(C0)2]4As2,synthesis, 4284 Cp2Fe2(p-C0)2(p-Si(2,4,6-i- (Cp*Mn(CO),(H)J,(p-SiH,), synthesis, Pr3C6HZ)2],~tr~~t~reand bonding, 42242 42268 c~MnFe,(co)~(PPh),synthesis, 4285, 109 CpzFe,(p-C0)2(p-SiR2), structure and bond- [Cp’3Mn3(NO)3(NH)]+,synthesis, 4296 ing, 42266, 268 [CpMolZAss,structure and bonding factors, (Cp*Fe)2(P2)2,structure and bonding fac- 4264 tors, 4252 [CpMo],(As,)(AsS), structure and bonding Cp*FePSTa(Cp2”),synthesis, 4290 factors, 4259 Cp, Group 4 metal-alkyl complexes Cp*,Mo3Co2(CO)lO(m5-N), synthesis, applications, 32370-381 4294 background, 32325-327 [CpMo(C0),I2P2Ph2,synthesis, 4293 base-free Cp2M(R)+systems, structures CpMoFeCo(CO)8AsMe, synthesis, 4293 Of, 32:347-348 [(C~~Mo~Fe(C0)~(p~-Se)l,synthesis and P-H elimination, 32356-360 structure, 4k293, 296 cationic hydrides, synthesis of higher com- [(CP~MO~F~~(CO)~(~~-S~)~],synthesis and plexes, 32:336-337 structure, 4k293-295 cationic metallacycles, coupling chemistry [(CP~M~ZF~~(C~)~(EL~-S~)(~L~-S~),I,synthe- of, 32374-378 sis and structure, 4k293-294 Cp2M(R)+complexes [(Cp2M02Fe(C0),(p3-Te)],synthesis and protonoloysis routes, 32332-335 structure, 4k296-297 synthesis of, 32329-337 [(Cp2Mo2Fe2( CO)6] (p4-Te)(p3-Se)(p3-S)], Cp2M(R), complexes, M-R bond cleav- synthesis and structure, 4k297, 299 age, 32330-332 Cp*,Mo,(P),, structure and bonding fac-

CpzM(R) (L) + complexes, synthesis of, tors, 4246 32329-337 Cp2MoP2H2, structure and bonding factors, Cp,M(R)(THF)+ complexes, structures, 4248 32337-339 C~MOP~,(CO)~(PP~~),AS,synthesis, 4291 Cp’2Zr(CH2CH2R)(L)+complexes, inter- Cp2M(R)+complexes actions in, 32341-343 applications CpzZr(CH,Ph)(L)+ complexes, structure cationic metallacycles, coupling chemis- of, 32:339-340 try of, 32377-378 Cp2Zr(R)(L)+complexes, bvonding inter- ligand C-H activation actions, 32346-347 catalytic coupling, 32379-380 insertion chemistry, 32352-355 NMR data, 32380 Cp,M(R)+ complexes 78

side reactions, 32381 protonolysis routes Zicglcr-Natta catalysis BPh4- aryl C-H bond activation, active species. 32370-372 32333 dumina catalysts, reactions with, C_p,.M(Me)' species, formation of, 32372-373 32334 alumoxanc catalysts, reactions with, [ Cp2Ti(Me)(NH >)]X,32332 32370-373 main group dicarbollide compounds, MgCI2 supported catalysts, 32333 32372-373 NMR studies, 32333-334 olefin polymerization activity, fea- Cp,M(R)(L) complexes, applications tures, 32373-374 cationic metallacycles, coupling chemistry reactivity considerations, 32371 of three coordinate cation, 32371 electronic effects, 32576 reactivity four membered, 32377-378 P-H elimination, 32356 NMR studies, 32374-376 Lewis acid-base chemistry, 32350 a-olefin insertions, 32:374-375 ligand C-H activation steric effects, 32374 ( C5Me5),Zr(Me)+,32362 three membered, 32374-377 Cp2Zr(Me)' , 32365 X-ray analysis, 32374-375 ortho w. alkyl, aryl bonds, 32345 ligand C-H activation, 32378-381 three vs. four, five membered metal- Ziegler-Natta catalysis, 32371-374 lacycles. 32365 CpzM(R)(L)+complexes olefin reactions reactivity a-olefin insertion, 32:366 propylene polymerization, 32369 f3-H elimination Turner-Hlatky zwitterion, 32568 activation entrophy, 32359 Zr-R bond hydrogenolysis, bis-MeCN complexes, formation of, 32360-362 32359 structures kinetic studies, 32358-360 bond angles, 32347-348 ligand effects, 32360 CH2CH(AIEt2)*ligand, distortion of. mechanism, 32359-340 32347 rates of, 32357 CP2Zr framework, 32347 insertion chemistry Eisch cation, 32348 alkyne insertion, 32353 nonclassical bonding interactions, azaalkenylidene intermediate, 32347 32354-355 Sinn-Kaminsky complex, 32347 early-metal hydrides. high reactivity, Turner-Hlatky zwitterionic compound, 32353 32348 ethylene polymerization, 32352 synthesis ketone insertions, 32352 Al-free routes, 32329 MeCN insertions, 32353. 355; kinet- [ CpJrI [CIHFI ics of, 32354; mechanism, 32354 ionic structure, 32329 nitrile insertions, 32:353 X-ray analysis, 32528 NMR studies, 32353-354 M-R bond cleavage propylene oligomerization, 32:352 BH4 requirement, 32328 reactivity, 32352-354 electron transfer rate, 32332 THF inhibition, 32352 general trend, 32331 Ti systems, 32354-355 one electron oxidation, 32331 Lewis acid-base chemistry rcductivc elimination, 32331 cationic Ti complexes, 32351 79 [Cp2Ti(m-SiH,)],

do metal isocyanide complexes, spectroscopic data, 32339-340 32351 THF ligand, replacement of, 32339 halide salts, addition of, 32350 X-ray structure, 32340 iminoacyl complexes, 32351 Cp2Zr(R)(L)+complexes, bonding ligand exchange reactions, 32351 Ca-interactions, 32346-347 ligand substitution, 32:349-350 B donor interactions, 32346 NMe3, reactions with, 32351 ligand displacement, 32346 nucleophilic attack, promotion of, strengths, 32:346-347 32:350-351 Zr-Ph interactions, 32:346 nucleophilic ring opening, 32351 electronic, 32326 salts of cations, 32350 Zr- P-CH2-Si interactions THF exchange, 32349 bonding, 32345 THF ring opening, 32351 electronic distortion, 32344 ligand C-H activation ligand substitution, 32345-346 general trend, 32364-365 NMR spectra, 32344-345 a-picoline, reaction with, 32362-363 steric interactions, 32344 requirements for, 32364-365 vinyltrimethylsilane, 32343-344 selectivity of, 32364-365 X-ray analysis, 32344 X-ray structure, 32:363 synthesis of olefin reactions A1 free routes, 32:330-335 ethylene polymerization, 32366-369 BPh4- requirement, 32330 ethylene shemistry, 32:366-369 from cationic hydrides NMR studies, 32366-367, 369 higher alkenyl complexes, propylene polymerization, 32369 32336-337 THF inhibited polymerization, higher alkyl complexes, 32336-337 32366-367 higher ally1 complexes, 32336-337 Ti vs. Zr systems, 32368-369 substrates activated, 32326 Cp2MR2,M-R bond cleavage of, Zr-R bond hydrogenolysis 32330-332 excess PMe3, reaction with, 32361 from neutral Cp2Zr(R), complexes, H2 reactions of, 32360 32330 a-bond metathesis reactions, one electron oxidation, formation in- 32:360-362 volving, 32330-331, 335 trend in reactivity, 32361-362 protonolysis routes, 32332-335 structures of titanacyclobutanes as precursor,

Cp2M(R) (THF) + complexes 32331-332 bond lengths, 32:338-339 Zr-R bond cleavage, ease of, 32331 characterization, 32337-338 Cp*Nb(CO)Z, structure and bonding fac- comparisons, 32338 tors, 4252 M-0 B bonding, 32:338-339 Cp2NizRu3(CO)9(PPh) X-ray structure, 32:337-338 structure and bonding factors, 4228 Cp',Zr (CH2CH2R) (THF)' synthesis, 4283 agostic interactions, 32:341-343 (C~*RU(~-~~-HS~C~M~)]~(,U-H)(H),synthe- distortion, degree of, 32:342 sis, 42244 isomers, 32343 (Cp*Ru(p-~1~-HsiR~))~(p-H)( H), fluxional isotope perturbation effects, 32342 behavior, 42279 NMR studies, 32341-342 Cp*2Ruz(pSiPhOMe)(p-OMe)(p-H),isom- PMe3, exchange with, 32343 erization, 42284 X-ray analysis, 32341 [Cp*,SmIZBiz,synthesis, 42112 CpzZr(CH,Ph)(L)+ complexes (CpzTi(m-SiH2)],, synthesis, 42375 80

[CpTi],P(,, structurc and bonding factors, Cryptands, effect on nucleophilic displace- 4267 ment at silicon, 20282, 293-294 CplZrBu2, decomposition, 42378-379 Crystal graphite flakes, 2888 [CpzZrI2PZ,synthesis, 4280 Crystallography Cp*2Zr2PzH2,structure and bonding fac- of agostic interactions, 28318-319 tors, 4248 of alkali GIC, 2892-93 Cp*zZr(PPh)3,synthesis, 4280 alkynyl-metal complexes, 38:90-120 CpzZr(P,(P(SiMe&), synthesis, 42103 CsCSH,, structure, 43295 C-R bond, 38116-117, 136-137 Cs(ChHh)3c(SiMe3)3rsynthesis and struc- CrCoz(CO)I,PH, synthesis, 4285 ture, 43285 [Cr(CO),( q6-C6H(,)],nonlinear optics, [CS(C~H~M~~-~,~,~)-J~F.~-M~CN]~,struc- 42352 ture, 43337 [(Cr(C0)s]4Te2]Z~,synthesis and structure, CsCMezPh, synthesis, 43:275 4k258-259 Cs2C2Ph4,synthesis, 43275, 277 [ (Cr4(CO)18(p3-Te,]2, synthesis and struc- CsLa(OC6H3Me2-2,6),, structure, ture, 4k257-258 4&335-336 [(Cr(CO)5)4Te3][PPh4]Z,synthesis and struc- [CS~(P~~C=CHCH=CP~~)(OCHZ- ture, 4k258-259 CHZOCH,)2(diglyme)z],synthesis and Cross-conjugated dienyltricarbonyliron cat- structure, 43317 ions, 26:148-149 [C~2(Ph~C=CPh~)(diglyme)~].synthcsis and structure, 43317 reactions with methanol, 26:148 [Cs(PhCH2),GaF)l2, structure, 43337 Cs(PhCH&InC1.0.5toluene, structurc, protonation, 26:148-149 43337 Cross-conjugation, 39:365 Cubanes, 371 Cross coupling, of ally1 and alkyl groups, crushed, 37:12-14 computer representation, 26.202-209 electronic absorption spectra, 3221-23 diamagnetic nickel intermediates, 26207 octagermacubane, 322,17-19 electron-transfer-catalyzed mechanism, octasilacubane, 321-4, 14-17, 36 26:203, 208-209 octastannacubane, 3219-22 one-electron nonchain sequences, 26:203, Cumulated unsaturated systems, reactions 205 with Grignard reagents, 7:4 paramagnetic nickel intermediates, Cumulene, reaction with disilcnes, 39258 26:206-207 Cumulene-transition metal complex, see radical-catalyzed mechanism, 26:203-207 Strained cyclic cumulcne-transition two-electron mcchanism, 26203-204 metal complex Cross-coupling reactions, via organonickel CUdPPh3)h(PPh)6 complexes, 17209-215 structure an bonding factors, 4231 a-Crotyl complexes. in ethylene-butadiene synthesis, 4281 codirnerization Cugh(P( SiMe& Jh(PEt3)IxP30. structure and as catalysts, 12283-290 bonding factors, 4241 nickel, 12292-293 (Ch2Xs)2Hg,arylation with, 28226-227 rhodium, 12272-273, 275-271, 281 Cyanamide stability and 1.4-hexadiene formation, from azides and isocyanides, 1k61 17:275-277 dialkyl, metal complexes, 1k151 Crown ethers reaction with effect on phenyl migration vs. cleavage of disilenes, 39:258 benzyl groups, 16204-205 Fe(CO)S, 10163 in phase-transfer catalysis, 19:183-186, clusters, 280-81 189, 191-200 , see also Pseudohalides 81 Cycloaddition reactions

metal carbonyl complexes, 10:173 divinylcyclobutanes, methyl derivatives, properties, 5208-210 870-72 Cyanide, see also Pseudohalides methylcyclooctadienes, 867-70 properties, 5201-207 Cyclic polystannanes, synthetic routes, Cyanide ion, induction of carbyne carbon- 33183- 184 ylation in ketenyl complexes, 2857 structural data, 33186 Cyanoacetates, metal, thermal decarboxyl- 1,2,3-tristannapropanes,33184 ation, 25246 Cyclic voltammetry Cyanoalkyl complexes, by insertion of tetra- of double-layered ruthenium complexes, cyanoethylene into metalcarbon bonds, 29224,226-227 l2:7 1 metal-alkynyl complexes, 3889-90 Cyanocobalamin, 16275 of triple-layered cyclophane complexes, Cyano complexes, of metal carbonyls, 29227-228 10168-173 Cyclization Cyano derivatives, of anionic transition acyloxysilanes via hydrosilation, 12419 metal hydrides, as catalyst, 27:44 dienes via nickel catalysts, 12125-128 Cyanoethynyl ligand, 38111 haloketones, a301 Cyanometal carbonyls, 818-19 Cyclization-cleavage rearrangements, of or- Cyanometal complexes, 3881, 112-114 ganomagnesium compounds, a-Cyano radical, reaction with Sn hydrides, 16132-160 M96 Cycloaddition reactions, 26325-329, 37:108 C,Y-chelating ligands, see Organotin chem- arsasilenes, 39224 istry [2+2] cycloaddition, 3922.5 Cyclic arsines, see also Organoarsenic com- disilenes, 39:2.55-262 pounds [2+1] cycloaddition, 39259-261 resolution, 4215-219 [2+2] cycloaddition, 39255-258 UV spectra, 4225-227 germanium doubly bonded compounds, Cyclic and chelated organometal amide, alu- 39295-301,320 minum, gallium, indium, and thallium iminosilanes, 39:173-174 bonding, 3k276 [2+2] cycloaddition, 39175, 180 chelating macrocycle, 3k276 [2+3] cycloaddition, 39173 equilibrium, 3k274, 276 [2+4] cycloaddition, 39180 intermolecular chelate, 3k274-275 phosphasilenes, 39216-219 isomeric form, 31:276 [2+2] cycloaddition, 39:212, 219 mono-metal centered ring, 3k274-275 [2+3] cycloaddition, 39:216-217 ring dimer, 31:273 [2+4] cycloaddition, 39214 Cyclic compounds, synthesis by nickel-cata- silaamidide formation, 39188 lyzed reactions, 8:48-83 silenes, 39:111-122 Cyclic condensation with carbonyl groups, 39122-128 of acetylenes to arenes, 1349 [2+1] cycloaddition, 39130-132 of 2-butyne on diphenylmanganese, [2+2+2] cycloaddition, 39120-121 1390-91 [2+2] cycloaddition, 39104, 121-122 Cyclic disilanes, metal-catalyzed redistribu- [2+3] cycloaddition, 39103, 133 tion reactions, 19229 [2+4] cycloaddition, 39120-121 in presence of acetylenes, 19229-230 ene reactions, 39:114,117, 128-130 CycIic hydrocarbons with imines, 39128 IR and Raman spectra, k254-255 silylenes, 39252 synthesis, 848-74 tin doubly bonded compounds, cyclooctadienes, substituted, 872-74 39314-317 1,9Cycloaddition reactions 82

1,3-Cycloaddition reactions, a-heterodiazoal- by ligand transfer, 4:108-111 kanes, 9412 properties, 41 12-1 16 Cycloadditions as reaction intermediates, 4138-139 + 21 reactions, 4:llY-135 to carbon-heteroatom triple, bonds, with donor ligands, 4:126-129 44A91-292 halogenation, 4129-130 carbonyl derivatives, 44:190-191 ligand transfer, 4:108-111 to multiple bonds, 44.189-190 with nucleophiles, 4130-133 [2 + 21, digermenes, M135-136 oxidation, 4125-126 [2 + 41, reaction with digermenes, reduction, 4123-125 44.136-137 substitution, 4:133-135 of carbenoids to aromatic carbon-carbon thermal decomposition, 4:119-123 bonds, 1297 redistribution reactions, 2311 1-1 12 of chlorosulfonyl isocyanate to propargyl , 4117 complexes, 1276 spectra, 4:118 by free ketenes, 2866 stability, 41 16-1 17 with iron-graphite, 28124 a-Cyclobutadiene complexes, 12.21-22 by ketenes, 2854 of cobalt, 12359-363 of ketenes with courdinated Ijgands, intermediates in formation, l2:363 288-9 mass spectra, 6285, 301 Cycloalkane derivatives, of platinum, Cyclobutadiene derivatives, 496-98 22148-158 dimethylenecyclobutene formulation, 496 Cycioalkylboranes, pyrolysis, 2288 tetramethylenecyclobutene formulation, Cyclobutadiene 496 attempted synthesis, 496-97 n-Cyclobutadiene-n-l,2-dicarbollyl- metal complexation, 2k77 palladium complex, 8:99 in metallacycles, 2697-124 Cyclobutadiene iron tricarbonyl, 279 MO treatment, 497-99 electrophilic substitution, 4139-141 stabilization by complex formation, oxidation, 4:140-141 498-99 synthesis, 4103 tetraborane analogy, 21:77-79 ?r-Cyclobutadiene metal complexes, mass Cyclobutadiene complexes, 495-141 spectra, 8231, 266, 275, 281 bonding, 4:lOl-102 a-Cyclobutadiene palladium complexes, cobalt, 416,113, 124, 135-136 10390 electron-transfer reactions, 2339, 60 solvent effects on reactions, 1&381 by insertion of metal atoms into carbon- transfer of ligands, 10:378-383 halogen bonds, 1582-83 Cyclobutadiene silver nitrate, 4135 iron, 499-100, 113, 115, 125-126, Cyclobutane 139-141 oxidative addition, computer representa- molybdenum, 4:114 tion, 26176 nickel, 4100-101, 113-114, 120-121, synthesis with phosphaalkenes, 41:13 123-125 Cyclobutenones, in vinylketene synthesis, palladium, 41017 106-108, 114-135, M302-307 122-125 n-Cyclobutenyl complexes, 4107- 108 preparation, 4102-111 cly, rrans-1,5-Cyclodecadicne from acetylenes, 4104-106 Cope rearrangement to cis-1,2-divinyl- from a-cyclobutenyl complexes, cyclohexane, &63 4107-108 synthesis from ethylene and butadiene, from 3.4-dihalocyclobutenes, 4103-204 859-63 from heterucyclopentadienes, 4107 Cyclodextrins, 38:181-182 Cyclohexene

Cyclodienes, hydroboration, 2279-280 platinum, 4362 Cyclodigermazane, 39294 tungsten, 4355 Cyclodisilatetrazanes vanadium, 4360 crystal structures, &35-36 Cycloheptatrienone, see Tropone synthesis, &33-34, 37 s-Cycloheptatrienyl complexes, mass spec- Cyclodisilazanes, 39162 tra, 8216, 223, 226, 232-233 1,3-Cyclodisiloxanes, 39262, 265-266 Cycloheptene complexes, 4365-366 Cyclo-1,3-distannoxane, 39318 manganese, 4366 1,5,9-Cyclododecatriene palladium, 4365 by nickel-catalyzed butadiene cyclization, silver, 4365 12142, 291 a-Cycloheptenyl palladium complexes, selective hydrogenation 4365 by rhodium catalyst, 12332 1,3-Cyclohexadiene by ruthenium catalyst, 12325 cocondensation with ruthenium, 29237 synthesis, 850-54 photochemical reactions with carbonyl Cyclododecatriene nickel, 240-41 complexes Cyclogermanes, 440 of chromium, -298,326-327, 329 1,2-Cycloheptadiene, transition metal com- cycloaddition to 1,3,5-cycloheptatriene, plexes 26331 reactivity, 42206-207 with decacarbonyldirhenium, 26367 synthesis, 42204-206 of molybdenum, -299,345 1,3-Cycloheptadiene, in photochemical reac- of tungsten, 26341, 351 tions with metal carbonyl complexes Cyclohexadiene complexes, 397-98 chromium, 26316 Cyclohexa-1,4-diene complexes, of palladi- molybdenm, 26348 um(I), 13369 Cycloheptadiene complexes, 399 s-Cyclohexadieneiron tricarbonyls, mass Cyclohepta-1,3-diene complexes, 4364-365 spectra of substituted, 8266-269 iron, 43.58, 364 Cyclohexadienyl complexes, 3129-132, 149 palladium, 4364 a-Cyclohexadienyl complexes ruthenium, 4364 iron, 1399-100 s-Cyclohepta-2,4-dienyl palladium com- manganese, 13:91-93 plexes, 4364-365 molybdenum, 1370 Cycloheptadienyne, transition metal com- rhenium, 1391 plexes, 42:192-197 rhodium, 13112 1,2,4,6-Cycloheptatetraene,transition metal ruthenium, 1394 complexes Cyclohexadienyl ruthenium complexes, fluxionality studies, 42212-214 29:213 reactivity, 42214-215 Cyclohexadine derivatives, dehydrogena- structure, 42208-209, 214-215 tion, 29164 synthesis, 42208, 210-212, 216 Cyclohexanes, catalytic reactions with plati- Cycloheptatriene, 39386 num catalysts, 38167-170 reaction with metal atoms, 1576-77 Cyclohexanone substitution in Group VI metal com- coupling with Ti-gr, 28127 plexes, 10364 oxidation by thallium(II1) salts, Cycloheptatriene complexes, 3:99, 1k19S-198 4355-363 Cyclohexasilane, 3833, 36 chromium, 4355-356, 361 Cyclohexasilanyllithium, 3832 iron, 4:358 Cyclohexastannanes, 38221,228 molybdenum, 4355-356 Cyclohexene reactions, 4356 oxythallation, 1k183 Cyclohexene 84

stereochemistry, 1k183 ring inversion, 31:246 Cyclohexene oxide, reaction with disilenes, polynuclear complexes, 19:180 39:262 Cyclooctatetraenc complexes, 399-100, Cyclohexyl isocyanide 106, 161,4375-380 addition to methylpalladium complexes, bonding, 4575 1k33 cobalt, k379 metal complexes, 1154 copper, 4377 Cyclohexyne, transition metal complexes, cycloaddition reactions, 1529 42180-191 cyclopentadienyltitanium, 9171 Cyclometallation iron, 4378-379 bipyridyl(bpy), 3442-43 manganese, 4380 palladium(I1) complexes, 3439-42, 46 molybdenum, 4380 platinum(I1) complexes, M42-46, 48 neptunium, 9390 platinum(1V) complexes, 3452 nickel, 4380 pyrazole, M39 nonrigidity square planar palladium(I1) complexes, iron, 16234-236 348 molybdenum, 16222-224 square planar platinum(I1) complexes, nickel, 16340 34:s ruthenium, 16:217, 236, 340 Cycloocta-1,3-diene, isomerization platinum, 4377 by , 4374 rhodium, 4378-380 by rhodium(II1) chloride, 4372-373 1,2-sigmatropic shifts in q4-derivatives, 1,s-Cyclooctadiene 1528-29 by nickel-catalyzed butadiene cyclization, and Woodward-Hoffmann rules, 17: 142 1528-29 bis-nickel complex and ethylene-butadi- silver, 4376 ene codimerization, 12295-298 synthesis via metal atoms, B77-78 1S-Cyclooctadienc, synthesis, 854-59 chromium, 1577 metal complexes, 8:277 uranium, 1577-78 Cycloocta-1,5-diene complexes, 4369-375 , 9:388 copper, 4373 titanium, 4380 gold, 4373 tungsten, 4380 iridium, 4372 uranium. 9385-386 metal carbonyls, 4374 valence tautomerism, 4378-379 osmium, 4372 Cyclooctatetraene compounds, of alkali met- palladium, 4369-370 als, 27203-205 platinum, 4369-370 Cyclooctatetraene-iron carbonyl complexes rhodium, 4:370-371 diiron hexacarbonyl, 15-6 ruthenium, 4372 iron tricarbonyl, k5-6, 12-13. 20, 22-23, silver, 4:373 28-29, 31 ~-Cycloocta-2,4-dienylpalladium com- Cyclooctatetraene-iron tricarbonyl, proton- plexes, 4370 ation, 8:147-148 Cyclooctatetraene Cyclooctatetraene-metal complexes, spec- metal complexes, 8233, 269,271 tral studies, k306-307 metallation Cyclooctatetraene-nickel complex, 240-41 7'-cyclooctatetraenyl ligand, 3k245 Cyclooctatetraenyl anion, spectral studies, isodynamical process in substituted k304-306 system Cyclooctatriene, equilibria and tautom- bond shift, 3k246 erism, 4380 NMR study, 3k247 Cyclooctatriene complexes, 3100, 156 85 Cyclopentadiene iron carbonyl derivatives

Cycloocta-1,3,5-triene complexes, 4381 of cyclopentadienyl-metal compounds, Cycloocta-l,3,6-triene complexes, 4381-383 2366-375 cobalt, 4383 from dicyclopentadiene, 2367-368 molybdenum, 4382-383 Cyclopentadiene, derivatives silver, 4381 bulky cyclopentadienes, concepts tungsten, 4382-383 chirality, 33346-351 Cyclooctatrienone-iron complex, 4383 kinetic stabilization, 33317-326 Cyclooctene, catalytic dimerization, novel molecular structures, 33326-341 17A14-117 rotation dynamics, 33342-346 Cyclooctene complexes, 4383-384 cyclopentadienyl metal complexes, manganese, 4384 33310-316 palladium, 4384 cyclopentadienylcobalticinium, 33313 platinum, 4383 decabenzylferrocene, 33315-316 silver, 4383 decaethylferrocene, 33314 n-Cyclooctenyl-nickel complexes, 833-34 halogen-lithium exchange, 33314 carbonylation, 834 hexakis(trimethylsilyl)ferrocene, 33316 coupling reactions, 834 1,1',2,2',4,4'-hexakis(trimethy1silyl) Cyclooctyne, 39212 stannocene, 33313 transition metal complexes, 42197 pentaphenylcyclopentadienyl, 33311 Cyclooligomerization photochemical rearrangement, 33315 acetylenes, 14262, 1R106 tantalum cyclopentadienyl, 33% 1-312 allenes, 14:270-278 template synthesis, modes of, butadiene, 17:106 33311-315 hydrogenation of product, 17:365 transition metal induced re- butadiene, catalyzed by supported nickel arrangement, 33315 complexes, 19218, 226 tungsten perethylcyclopentadienyl, olefins, 17:106 33311-312 Cyclopentadiene, 26127 supracyclopentadienes, synthesis of, annulation to enamines, 4k176-177 33300-310 manganesepentacarbonyl alkyl reaction, pentabenzylcyclopentadiene, 37:200 33303-304 pentacarbonylrhenate reaction, 37:239 pentakis(methylthio)cyclopentadiene, reactions with 33306,309 acetylcarbonyl- v4-cyclopentadiene-qs- penta(methoxycarbony1)cyclopenta- cyclopentadieny lmolybdenum, diene, 33309-310 26345-346 pentaphenylcyclopentadiene, basic metals, 2370-373 33301-302 metal carbonyls, 2373-375 perethylcyclopentadienes, 33306, 308 nickel carbonyl, 212-13 perisopropylcyclopentadienes, chromium hexacarbonyl, 26298 33306-307 decacarbonyldirhenium, 26367 tetraphenylcyclopentadiene, 33301-303 dimethylmagnesium, 26233 triphenylcyclopentadiene, 33303 metal atoms, 1970-71 tris(trimethylsilyl)cyclopentadiene, phosphasilenes, 39:212-213 33304-305 silenes, 39113, 115 tri(tert-butyl)cyclopentadiene, substituted chromium carbonyls, 26:326 33305-306 thallium vapor, 26:253 Cyclopentadiene complexes, 394-96 tricarbonylcyclopentadienylmethylmo- Cyclopentadiene iron carbonyl derivatives, lybdenum, 26:336-338 k23-25 synthesis, 4k197-198 dienyl-iron carbonyl cation, k31-33 Cyclopentadiene iron carbonyl derivatives 86

reaction with fulvene, 1:36 oligomeriza tion, 30:68-69 Cyclopentadicnides, with metal compounds, of dimethyl acctylenedicarboxylate, 2375-382 3069 Cyclopentadienone, as ligand, 5101-104 of hexafluorobut-2-yne, 30:69 structure, 5102 orthometallation, 30:70-73 Cyclopentadienonc, carbonylation of al- intermolecular, 3072-73 kynes, 24 intramolecular, 3070-72 v-Cyclopentadienonecobalt complexes, mechanism, 30:70 12:35Y -363 phosphine exchange, 308-16 intermediates in formation, 12363 preparation, 302-4 structure and bonding, 12363-366 fulvalene, 303 a-Cyclopentadienyl/u-alkyl bi- and trimetal- halide, 302-3 lic complexes, 32275-288 nitrosyl, 304 Cyclopentadienylaluniinum complexes, reaction with electrophile, W.25-30 26242-243 acid, 3026-27 Cyclopentadienyl anion, spectral expecta- chelating diphosphine, 3027 tions, k262-264 complexing, 3026-27 C:yclopentadicnylberylIium bromide, equilibria data, 3026-27 26228-229 noncomplexing, 3026 Cyclopentadienylberyllium chloride, insertion, 3027-29 26228-229 carbon disulfide mechanism, crystal structure, 26287 3027-28 Cyclopentadienylberyllium complexes, stannous chloride mechanism, 26:226-23 1 30~28-29 structures, 26228 $unsaturated ligand, 3066-68 Cyclopentadienylberyllium hydridc, Cyclopentadienyl bistriphenylphosphinc ru- 26:228-229 thenium complex, exchange reaction Cyclopentadienyl bisphosphine ruthenium halidc for alkyl, 30:17-21 complex alkyllithium reagent, 3020-21 acetylide. see Ruthenium, acetylide com- Grignard reagent, 3017-20 plex. cyclopentadienyl bisphosphine halide for halide, 3016-17 allenylidene, see Ruthenium, allenylidene mechanism, 30:16-17 complex, cyclopentadicnyl bisphos- halide for hydride, 30:21-23 phine Grignard reagent, 3021 bridgcd diruthenium, 3013 lithium aluminum hydride, 3021-22 carhene, see Ruthenium, carbene com- reverse reaction, 3022-23 plexes, cyclopentadienyl bisphos- sodium methoxide, 3022 phinc halide for neutral two-electron donor, decomplexation reaction, 3064-66 3023-25 hasc, 3065-66 dissociation rate, 3023-24 halogen, 30:64 mechanism, 3023 hydrochloric acid, 3065 stereochcmical consequence, 3024 mercuric halide, 3064 tridentate ligand, 3024-25 oxygen, 3066 lability, 308 geometry, M4-7 phosphine for C, N, and S donor ligand, bond angle, 305-7 3012-16 chelating diphosphine, 306-7 N-heterocyclic base, 3013 steric strain, 305 isocyanide, 30:12-13 structure, 305-7 tetrathiometallate, 3015 halide exchange. 3016-25 thiocarboxyamide, 3014-15 a-Cyclopentadienyl complexes

thiophene, 3016 pentacarbonyls, 29:105-106 phosphine for carbonyl, 3011-12 tetracarbonyls, 29106-110 carbonylation, 3011 tricarbonyls, 29111 - 112 iron carbonyl, 3011 systems related to Cp2M2(CO),, 29117 stability, 3012 c5-(Cyclopentadieny1)carbonyl- sulfur driven, 3011 triphenylphosphine iridium, 32205 phosphine for phosphine, 308-1 1 E'-( Cyclopentadieny1)carbonyl- chelated derivative, 309-11 triphenylphosphine rhodium, 32205, diastereomer, 3010 212 racemic mixture, 309 a-CyclopentadienyUu-carbynehi- and trime- Cyclopentadienylboron complexes, tallic complexes, 32290-291 26238-239 Cyclopentadienyl complexes, 3:114-127 n-CyclopentadienyUu-carbene bi- and trime- bisphosphine ruthenium, 301-76 tallic complexes, 32288-290 cyano-bridged, 3017 Cyclopentadienyl carbonyl complexes hydride, 30:22-23,27-28 reactions isocyanide, 30:17 with alkynes, 29147-148 isoelectronic, 30200-208 cluster formation, 29149-150 isonitrile, 3017 with diazoalkanes. 29144-147 metallocene, 30200-204, 216 with heteroalkynes, 29147-148 triple-decker sandwich, 30216-218 with other ligands, 29149 u-a rearrangement, 16246 with radical anion, 29151-154 spectral analysis, k256-257 reactions of pentacarbonyls, 29121-122 o-Cyclopentadienyl complexes reactions of tetracarbonyls, 29:123-144 actinides, 9382-391 addition of four-electron donor ligands a-arene iron derivatives, 1044-47, 85-86 alkynes, 29128-133 beryllium, 9205 four-electron thioketones, (CsH,) Co (C0)2,358-359, reaction with 29138-140 alkynes, 12:359-363 heteroalkynes, 29133-135 copper, 12228 isonitriles, 29135-138 IR spectra, 12:239-240 with ArN02, NOy, and NO, isocyanide derivatives as catalysts, 29142-143 12:308 cluster formation, 29143-144 structure, 12:239 with diazoalkanes, 29125-128 correlation between 'H and I3C chemical electrophilic addition of X2 and HX, shifts, U155 29140-141 formation of ferrocene from, 10083-384 with elemental sulfur and selenium, Group VII tricarbonyl complexes, 29141-142 1047-50 two-electron additions iron ''C NMR spectra, U.:143, 145, 148, carbonylation, 29123-124 182,187 isonitriles, 29124-125 lanthanides, 9367-376 phosphines, 29124-125 adducts, 9370-371 reactions of tricarbonyls, 29:144 chlorides, 9372-376 unsaturated, 29101-102 ligand transfer reactions, 10:383, 390 Cp2M2( CO),, 29~102 mass spectra, 6292, 299-300 general formula, 29101 organotitanium derivatives, 1050 stoichiometries and occurrence, structures, 594-98 29103- 104 titanium@), 9175-180 structures, 29105-117 titanium(III), 9152-171 dicarbonyls, 29113-117 bis compounds, 9152-160 a-Cyclopentadienyl complexes 88

mono compounds, 9:160-161, 170-171 Cyclopentadienyllead complexes, tris complex, 9;152, 154 26:279-281 uranium, 9:382 structures, 26:280 Cyclopentddienyl compounds, of alkali met- synthesis, 26:279%281 als, 21201-203, 243 Cyclopentadienyl ligand, 31152, 154 Cyclopentadienyl cyclooctadiene chlororu- abundance in synthetic organometallic thenium(T1) complex, 29187 compounds, &I17 nCyclopentadienyl-n-l,2-dicarbollyl metal acidity, 26126-127 complexes. 8:91, 96-97 in alkali metal complexes, 26:125-126 Cyclopentadienyldicarbonylcobalt, bonding modes, 26125-126 26:149-1.50 bond lengths, 26139 Cyclopen tadienyldicarbon ylmanganese, bridging, in dimethyl(cyclopcntadieny1)- 26149 aluminum, 26:242-243 Cyclopentadienyldicarbonyl ruthenium di- bridging, palladium-palladium bond, mer, 29188 19: 156-1 78 Cyclopentadienylgallium complexes formation from tungstenacyclobutadiene dialkyl dcrivatives, 26.245-246 alkoxide complexes, 27535-336 structure, 2624.5 Group 2 compounds Cyclopentadicnylgermanium cations, 26:265 chemical vapor deposition precursors, molecular orbitals, 26265 40311 reaction to form azincs, 26266 physical properties, 40:297-298 structurc, 26:260 synthesis, 40:292-293 synthesis, 26265 hydrogen orientation Cyclopentadienylgermanium chloride, in cyclopentadienylberyllium chloride, 26263 26287 calculated orbital energies, 26263 in indium complexes, 26:250 structure, 26260 in monocyclopentadienylberyllium com- vertical ionization energies, 26263 plexes, 26229 Cyclopentadicnylgermanium complexes, lithium complex, 26221-222 26258-266 in migratory insertion reactions, 26189 bis(trimethylsilyl)methyl derivative, molecular orbitals, 26156-157 26:263 molybdenum(TT)/ fluxionality, 26263-264 tungsten(I1)halocarbonyl complexes mixed transition metal complexes, 26:264 isomerization, 40102-103 molecular orbitals, 26260-265 reactions with neutral donor ligands, Cyclopcntadienyl Grignard reagents, synthe- &lo2 sis of cyclopentadienyl metal com- substituent effects pounds, 2380-382 melting points, 40:127-128 Cyclopentadienylidene, as six-electron do- oxygen sensitivity, &130-132 nor, 20183 volatility, 40:129-130 Cyclopentadienylindium complexes, synthesis, 40:101-102 26249-251 orientation bonding, 26250-251 in dicyclopentadienylberyllium, 26227 molecular orbitals, 2625 1 in dicyclopentadienylgermanium com- structure. 26249 plexes, 26258 synthesis, 26:250 in dicyclopentadienylmagnesium. Cyclopentadienyliron carbonyl anions, 26232-233 2229-233 in dicyclopentadienyltin complexes, Cyclopentadienyliron complexes, 31231, 26270 233, 276 in magnesium Complexes, 26233 89 n-Cyclopentadienylmetal complexes

in transition metal complexes, 26125-126 Cyclopentadienyllithium complexes, rotation barriers, 26:140 26221-222 Cyclopentadienyl ligand, with functional reaction with germanium dichloride, substituents, 2k1-55 26262,265 acid chloride, 215 Cyclopentadienylmagnesium bromide, tet- air-stability, 2k17 raethylethylenediamine adduct, 26233 aldehydes, 2k4-5, 14,19 bond length, 26234 amide, 215-6 Cyclopentadienylmagnesium n complexes, azo derivatives, 2k32 26232-236 cyanide, 2k5-6, 19 bis(tetrahydr0furan) adducts, 26232 dicyanides, 2k14-16, 19 ether adduct, &233 diesters, 2k13, 19 ionization energies, 2k235 diformyl, 2k14, 19 preparation, 26232-234 N,N’-dimethylamine, 2k30 structures, 26233 dimethylaminomethyl, 2k30-31 tetraethylethylenediamine adducts, 26233 fused lactone, 2k6 tetramethylethylenediamine adduct, halogen derivatives, 2k20-28 26233 from diazacyclopentadienes, 2k20-25 tris(trimethylsily1) adducts, 2k233-234 indenyls, 21:22 Cyclopentadienylmanganese tricarbonyl pentachlorides, 2k21-22 derivatives, 3:221-223 thallium salts, 2k26-28 substitution, 3219-220 metal complexes, 2k7-14 NMR spectra, 1089 monoesters, 2k4, 13, 19 organic derivatives, 1047-50 as weak electron donor, 1O:llO thallium salts, 2k5-6 a-Cyclopentadienylmanganese tricarbonyl, monoketones, 2k4 mass spectrum, 6288 by electrolysis of ferrocenes, 2k4-5 derivatives, mass spectra, 6306, 310 mononitrile, 2k6 Cyclopentadienylmetal carbonyls nitro derivative, 21:19-20, 28-30 derivatives, 3212-213 olefin derivatives, 2k39-46 spectral studies, k281-284 from fulvenes, 2k40-46 n-Cyclopentadienylmetal carbonyls, cationic polycycanides, 2k44-45 cobalt, 8155 from spirodiene, 2k43 Group VI, 8:134-137 in synthesis of organometallic mono- iron, 8:150-152 mers, 2k41-42 n-Cyclopentadienylmetal carbonyls, mass via tetracyanoethylene, 2k44 spectra, 6288, 299-300 pentacarbomethoxy derivative, 2k16-18 Cyclopentadienylmetal complexes metal complexes, 2k18 cyclopentadienyl anion, k262-263, 275 silver salt, 2k17 dicyclopentadienyls, 1:263-272, 276-282, thallium salt, 2k17-18 309 phosphines, 2k33-36 identifying Cp-M bond type, k289-291 metal complexes, 2k33-34, 36-38 monocyclopentadienyls, k269, 275-278, thallium derivative, 2k38 281-283 and pK, values of cyclopentadienes, parameters affecting spectra, k286-289 21:19 spectral anaIysis of C, systems, k259-291 polycyano derivatives, 2k14-16 tetrxcyclopentadienyls, k213-274 on polymer support, 2k46-51 tricyclopentadienyls, k272-273, 283 metal complexes, 2146-51 n-Cyclopentadienylmetal complexes silyls, 2k37-38 (C5H5)Mn(CO)3, lk217-218,230-231 triformyl, 2k14, 19 irradiation, 1k230-232 a-Cyclopentadienylmetal complexes 90 a-Cyclopentadienylmetal complexes, mass ring substituted, spectra, 1:284-286 spectra Cyclopentadienylsodium, Lewis base ad- chromium, molybdenum, and tungsten, ducts, 26224-225 8218-223 Cyclopentadienylsulfur complexes, cobalt, 8272-276 26286-287 iron, 8259-264 Cyclopentadienylthallium, 1k149-155 ferrocene derivatives, 8241-259 organic reactions, 11:153 manganese, 8234-239 preparations of matallocenes, 1k152-154 cymantrene derivatives, 8235-238 Cyclopentadienylthallium complexes, nickel, 8278-280 26252-255 palladium and platinum, 8280 pentachloro derivative, 26:253-255 rhenium and technetium, 8239-241 pentamethyl derivative, 26:253-254 rhodium and iridium, 8276-277 reaction with transition metal p complex, ruthenium and osmium, 8271 26:256 titanium, zirconium, and hafnium, silylated derivatives, 26253-254 8213-215 structure, 26:254 vanadium, 8216-218 synthesis, 26252-253 Cyclopentadienylmetal compounds tricyanovinyl derivative, 26254-255 applications of Cyclopentadienyltin complexes, 26:267-276 antitumor agents, 33324-325 cations, 26274-276 organomctallic liquid crystals, reactions with bases, 2627.5 33325-326 halides, 26274 from basic metal salts, 2372 structures, 26:271 from cyclopentadiene, 2367 Cyclopentadienyl transition metal com- from ionic cyclopentadienides and metal, pounds 2375-382 by addition reactions, 2385 nomenclature, 2366 from alkali metal cyclopentadienide and synthesis from cyclopentadiene, metal carbonyl, 2382 2:366-375 from alkali metal cyclopentadienide and cr-Cyclopentadienylmetal compounds, 2366 metal salt, 2377-379 Cyclopentadienylmetal hydrides, spectral from alkenes and alkynes, 2382-383 studies, k284-285 from cyclopcntadienyl Grignard and Cyclopentadienylmetal nitrosyl complexes, metal salt, 2380-382 7:224-229 by ligand displacement, 2385 Cyclopentadienylmetal tricarbonyls, substi- by neutron activation, 2:385 tuted derivatives, 2375 by oxidation, 2383-384 Cyclopentadienylnickcl carbonyl anion, from a-bonded cyclopentadienyl metal 2:250 compound, 2:383-385 Cyclopentadienyl nitrosyls, k284 preparation Cyclopentadienyl 0x0 complexes of mixed derivatives, 2382 parameters of M-0-M linkage, 28363 of substituted derivatives, 2378-379 synthesis, 28346-347 by reduction, 2383-384 Cyclopentadienyl(pentadieny1)iridium cat- table of properties, 2386-404 ions, 261.52-153 by thermal decomposition, 2384-385 Cyclopentadienyl(pentadieny1)rhodium cat- a-Cyclopentadienyl transition metal coin- ions, 26152-1.53 pounds, 2366 Cyclopentadienylruthenium carbonyl cr-Cyclopentadienyl transition metal com- anions, 2229-232 pounds, 2329-330 Cyclopentadienyls Cyclopentadienyltricarbonylmanganese, ring exchange, 37164 26149 91 Cyclotrisilane

Cyclopentadienyltricarbonylrhenium,26150 Cyclopropenium cation, k240 Cyclopenta[b]pyrans, synthesis, 4k199 spectra analysis, k257-258 Cyclopentasilanes, ring-opening polymeriza- a-Cyclopropenyl transition metal complex, tion, 3837-38 2355 Cyclopentasilanyllithium, 3833 Cyclopropylaluminum compounds, Cyclopentatriene, transition metal com- 8:183-185 plexes, 42200-201 Cyclopropyl Grignard reagents, re- Cyclopentene, manganesepentacarbonyl al- arrangement, 16131-135 kyl reaction, 32200 Cyclopropylmethyl radical rearrangement, Cyclopentenylidenes, synthesis, 4k192-193 26:197 a-Cyclopentenyl metal complex, 2348 Cyclopropyl radical, reaction with Sn hy- Cyclopentyne, transition metal complexes, drides, U94-95 42187-189 Cycloreversion, [2 + 21, 4-membered rings, Cyclopolystannanes, 38217-232 M116-117 Cyclopropanation, Simmons-Smith, ultra- Cycloreversion reactions, disilenes, by 237, sound application to olefins with zinc 39257 diiodomethane, 25108-109 Cyclosilanes, 47-11, 240 Cyclopropane chemical properties, k115-116, 136 analogy with p-methylene complexes, cleavage of ring, 431-35 20197 nomenclature, k93-94 from arsonium ylides, 20142-145 perphenylated, 1:94-103, 117-132 bonding, 1436 physical properties, k94 from carbene complexes and ethylvinyl preparation, k94, 110-115 ether, 1417 Cyclosilazanes, 9329-331 conversion to a-olefins via metathesis cat- cationic and dipolar isosteres, 9337 alyst, 17:462-463 four-membered rings, 9:329 in ethylene disproportionation, 12459 Cyclosiloxanes, 39181 in olefin metathesis, 17450, 459-468 Cyclotetragermanes, 326 carbene elimination, 12450 dimerization, 3214 oxidative addition of, computer represen- phenylated, 328 tation, 26176 ring structure, 329 platinum chloride complex, 326 synthesis, 328 synthesis via methylene shift reagents, Cyclotetrasilane, 3211, 133, 39238 18156-157 coupling, 37:14 optical yield, 18:156-157 ring-opening polymerization, 3837 via thermal decomposition of metalla- structure, 3211 cyclobutadienes, 1R456-457 synthesis, 328 Cyclopropane complexes, structure and Cyclotetrastannanes, 38207, 218, 221-226, bonding, 9112-114 228,230-231 Cyclopropane derivatives, synthesis Cyclotrigermanes, 326, 39287, 290 via copper carbenoids, E308-309 Cyclotrigermenyl radical stereospecific, 12:86-90 in digermene synthesis, 44:132 from zinc carbenoids and olefins, 1285 EPR study, U133 Cyclopropene Cyclotrimerization of alkynes, by cobalt car- insertion bonyls, 12:366-369 in synthesis of vinylketene complexes, mechanism of reaction, E369-371 U297 Cyclotrisilane in vinylketene synthesis, 44:308-319 photolysis, 39255 in vinylketene synthesis, 44:289-290, silyene-Lewis base complex synthesis, 300-301 4333-34 Cyclotristannane 92

Cyclotristannane, 3220, 38222-223, 226, intcrplane angles, 26:258 228, 230-232, 234, 39309 molecular orbitals, 26:262 Cyclotristannoxanes, 38230 reaction with electrophiles, 2&26S Cylcophane ruthenium complexes Decamethylsilicocene, siiyene-Lewis base double-layered, reduction and cyclic volt- complex synthesis, 4334 ammetry of, 29223. 225-227 Decamethylsilocene, 26288 synthesis, 29221-224 Decaphenylcyclopentasilane, 3832 triple-layered, cyclic voltammetry and re- Decaphenylferrocene, 33333 duction, 29227-228 synthesis, 40:123, 125 Cymantrene derivatives, mass spectra, Decaphenylgermanocene, 33332 8235-238 Decaphenylplumbocene, 33332 Cymantrenylmethylidyne complexes, 32291 Decaphenylstannoccnc, 333328-332 Decarbonylation acylmanganese carbonyl, 2:209-210 D coordinated ketenes, 2847-49 DANTE dimethylketene, 2814 magnetization transfer application, ketenes, 2812-13 28448-450 manganese alkylpentacarbonyls, 37:173 one-dimensional NMR spectroscopy appli- rhenium alkylpcntacarbonyls, 32176 cation, 2&422-423 in synthesis of cyclopentadienyl metal Davies-Green-Mingos rules, 3M30 0x0 compounds, 28345-346 d-block clcinents, terphenyl derivatives, Decarbonylation, acyl complexes, 1k92, M14-17 105-112, 114-117 Dealkylation, isocyanide complexes, 1k78 chemical methods, 1k111 Decabenzylgermanocene, 26:288 kinetics and mechanism, 11:105-110 Decabenzylmetallocenes, 33337-339 photolytic, 1k111 Decabutyltetrastannanc, 38:205 thermal reactions, 1k105-110 Decacarbonyldimanganese, reactions with ligand effects, 1k109 1,3-butadicne, 26353-354 solvent effects, 1k108-109 cumulated dienes, 26:358-365 Decarbonylation reactions 1,2-dimcthylallcnc, 26:362 catalysis by (Ph,P),RhCl, 288-89 1,3-pentadiene, 26354-358 computer representation, 26:178, 18Y-190 1,2-, 26:359 feasibility matrix, 26:190 Decacarbonyldirhenium Decarborane(l4), derivatives, 3302-305 bond enthalpies, 2641 Dccarboxy lation reactions with benzoates in presence of copper(1) oxide, acetylene, %366 a304 1,3-butadiene, 26:366-367 copper(1) carboxylates, 12226 1,3-cyclohexadiene. 26:367 electrochemically initiated, 25270 cyclopentadienc, 26367 heterolytic, possible mechanisms for, dienes, 26.365-369 25239-242 2-methyl-l,3-butadiene, 26367 homolytic, 25242-243 trienes, 26366 ketene, 3274 Decahydrohexaboranc, 2k75 nickel complexes, a73 Decahydropentaborate anion, 2k79-80 nucleophile-carbonyl adducts, 2&179-185 cyclopentadienyl analogy, 21:79-80 peroxide initiated, 25268-269 Decakis(2,6-diethylphenyl)dccastanna- photochemically initiated, 25269-270 [S]prismane, 37:20-21 radical initiated, 25268-270 Decamethylcyclopentasilanc, 38:33 thermal, see Thermal decarboxylation Decamethylgermanocene, 26:262 water gas shift reaction and, 28179-180 93 Dialkylzinc compounds

1,4,9-Decatriene Desulfination metal-catalyzed synthesis, 859-63 iridium complex, a51 via nickel-catalyzed reaction of ethylene iron sulfinates, l264 with butadiene, 1R291 metal sultine complexes, l257 Decatrienes, from styrene and butadiene, Desulfuration, graphite-alkali metals, 875-76 28104-105 P-Decay, chemical effects, 11:234-237 Dethallation reaction, lM17 Decomposition, 1,2-digermacyclobutane, Dewar benzene, 3R4 M130 metal complexes, 8231-232 Decoupling Dewar-Chatt-Duncanson model, 39216-217 broadband, using multiple pulses, allene-metal bonding, 14267 2lk423-424 metalolefin bonding, 13370 in magnetization transfer experiments, olefin-metal bonding, 1435, 1512, 14-19, 28:446-448 21,16:225,19267 Decoupling reactions, computer representa- v4-Dewar 1,3,5-triphosphabenzene complex, tion, 26:179 synthesis with phosphaalkynes, Defluorolithiation, germene, M118 4l5-52 Defluorosilylation, germene, a118 Diacetylbenzene, orthometallation reaction, Deformation vibrations, k243, 248-251 32186-1 87 Degenerate four-wave mixing, third-order Diacetylene 0x0 compounds, 28:353 nonlinear optics analysis, 43360-361 Dialanes, 3944 Dehalogenation 2,4-Dialkoxy-4-alkyl-1-chroma-l,3-diene,hy- dichlorodigermane, 44130-131 drochinone synthesis, 4k219 in synthesis of trimethylenemethane 2,4-Dialkoxy-4-pheny1-l-chroma-1,3-diene, metal complexes, 2%280-282 cyclization reaction, 4k218-219 Dehydroboration, 3:272 (Dialkoxysilyl)lithium, 38:20 Dehydrobufotenine, synthesis, 42:162 Dialkylalkenylborane, 2281 Dehydrocoupling Dialkyl aluminum chlorides, 35 catalyst development, 42401 Dialkylaminoboron derivatives general reaction, 42364 coupling with sodium-potassium alloy, heterodehydrocoupling, see Heterodehy- 10240 drocoupling metathetical reactions, 10242 homodehydrocoupling, see Homodehydro- Dialkylchalconides, 3872 coupling Dialkylcyanide-transition metaI complexes, thermodynamics, 42:365-366 2355-356 Dehydrohalogenation Dialkyldiaryldisilenes, 39240, 242, 249, 255 germanimines, M145-146 Dialkyldimesityldisilenes, 39248 germanium doubly bonded compound Dialkylgallium ligand, 3960 by, 39:288 Dialkylindium ligand, 3960 tin doubly bonded compounds by, Dialkylmercury compounds, 9200 39310-331 1,l-Dialkyl-1-silacyclobutanes,charge trans- Demethanative coupling, germanium-germa- fer complexes nium bond formation, 43246-248 ionization potentials, 34192-193 Demethylation, polysilanes, 6:20 spectra, 34192 Density functional methods, nonlinear op- tetracyanoethylene, mixtures with, tics, 42311-312 34192-1 93 Deprotonation, of metal acyl ligands, Dialkylstannylene, 39304 B26-27 Dialkyltin dihalides, preparation, 3869 DEPT, see Distortion enhancement of po- Dialkyl(trimethylsilyl)diaryldisilenes, 39:241 larization transfer Dialkylzinc compounds, 3859 Diallyldimethylsilane 94

Diallyldimethylsilane, pyrolysis, 3990 optical resolution, 18160-165 Diallyl ether 1 ,3-Diaza-2-boroline, 18322 asymmetric cyclization. 12135-136 Diazabutadiene complexes, 10154 isomerization via nickel catalyst, 1,4-Diaza-l,3-butadiene ligands, 2k151-239 1R126-127 activation on coordination, 2k217-233 Diallylplatinuni, 37229 catalytic reactions, 2k229-233 Dianiagnctism imidazoline formation. 21:217-219 fluorocarbon n-complex, k197, 199-200 oxidation, 2k219-221 a-bonded fluorocarbon transition metals, as bridging u-donors. 21:165-167 k195 structural data, 2k160-161, 165 Diamides, multiple bonding, 3918-26 as chelating u-donors, 21:158, 167-193 1,4-Diamino-2-alkoxynaphthalenes.synthe- bonding, 2k172-175 sis, 4k199-200 complex synthesis, 21:167-193 Diarsaferrocenes, 39:328 Raman spectra, 21:172-174 conformation, 39340 solvatochromism, 2k172-174, 178 clcctrochemistry, 39:343-344 structures, 2k160-163, 171-172, 177, molecular structure, 39333 190 reactions, 39345, 347 as eight-electron u,n-bridges, 2k158, synthesis, 39327 199-203 Diarsinc (o-phenylenebisfdimenthylarsine)) 'H NMR spectra, 2k199-200 complexes structures, 2k162-163, 199-202 chromium, 3204, 208 metal complexes, 2k156-234 halogenation, 3210-21 1 as catalysts, 2k233 iron, 3230-231 fluxionality, 2k210-212 manganese, 3217 NMR spectra, 21:209-211 molybdenum, 3:204, 208 radicals, 2k213, 217 halogenation, 3210-211 steric factors and bonding mode, nickel, 3249 2k157,203-208 tungsten, 3204, 208 X-ray structures, 2k160-163, 208-209 halogenation, 3210-21 1 as monodentate u-donors, 2k157-165 vanadium, 3195 inter- and intramolecular exchange, Diarsines, 4187-189 2k15Y, 162-164 conformation, 39340 structures, 2k159-161 Diarylacetylenes, synthesis via organocop- radicals, 2k213 per compounds, Kk273-274 ESR spectra, 2k213 Diarylbis(trimethylsilyl)disilene, 39:242 reaction with aluminum alkyl, 2k222-225 Diarylbis(trimethylsilyl)gerrnanes, 39287 as six-electron u,n-bridges, Zk193-199 Diaryldichlorogermanes, 39:290 fluxionality, 21:195-196 Diarylgermane, 39303 infrared carbonyl spectra, 2k199 Diarylgermaneselone, 39283, 290 NMR spectra, 2k197 Diarylgermanethione, 39283, 290 synthesis, 2k196-198 Diarylgermylene, 39287, 303 structures, 21:153-156 Diary1 mercury, by symmetrization reac- gas phase conformation, 2k153-154 tions, 103 MO calculations, 21:154 Diarylstannanethione, synthesis, 39312 photoelectron spectra, 2k154, 156 Diarylstannylene, 38218, 231, 39312 in solid state, 2k154-155 Diarylthallium compounds, 1k157-160 synthesis, 2k153 Diastereroisomers 1,4-Diazabutadienes, reaction with disi- chromatographic separation, 18165166 lenes, 39261-262 determination by NMR, 18152 Diazacyclopentadienes, 2k19-23 95 Diazo compounds

1,2-Diaza-3,6-diborine, 18303, 321-322 photoelectron spectra, 3469 Diazadiene ruthenium(0) complexes, 29175 general syntheses 2,3-1-Diazaferroles, M103-104 aryldiazonium group insertion, 3472 Diazagermylenes, 39289-290 hydrazine oxidation, coordinated, 3472 1,2,3-Diazaphospholes lead tetraacetate oxidation, 3472 metal coordination, 4M7-18 photochemical ligand substitution, synthesis with phosphaalkenes, 4k17 3171 Diazasilacyclopropane, synthesis, &28-29 thermal ligand substitution, 3471 Diazastannylene, 39312 Group IVB derivatives, see individual Diaza( trimethy lsilyl)methyIgermylenes, compounds 39289 modes of coordination Diazenes mononuclear s complex formation, complexes formed 3470-71 chromium carbonyl n2 orbital involvement, 3470-71 physical properties, 3480-90 polynuclear complex formation, reactivity, 3490-93 3470-71 synthesis, 3480-90, 93 structure, 23138-139 cobalt carbonyl, synthesis, 3493 Diazene-transition metal complexes, struc- iron carbonyl tures, 1457 physical properties, 3472-79 I ,2,3-Diazepinones, iron assisted synthesis reactivity, M79-80 of double addition, 32100, 34102 synthesis, M72-79, 93 irradiation, 3499-101 manganese, 3498 mechanism, 34.99-100 molybdenum carbonyl reactions, 34:98-99, 102 physical properties, 3480-90 X-ray analysis, 34102 reactivity, M90-93 Diazidogermacyclopentane, photolysis, synthesis, M80-90, 93 44:118-119 rhodium carbonyl, synthesis, 34:89 2,2-Diazidohexamethyltrisilane,photolysis, ruthenium carbonyl 39183 physical properties, 3478-79 Diazirine, complexes formed reactivity, 34:79-80 iron, 3495-97 synthesis, 3478-79, 93 ruthenium. 3497 silicon, 3498 titanium, 349.5, 97 titanium Diazoalkanes, 9415-429, see also a-Hetero- product formation, 3494-95 diazoalkanes reactions, M93 insertion into metal-halogen bonds, 9421 tungsten carbonyl metalation, 9400 physical properties, 3480-90 metal derivatives, reactions, 9401 reactivity, 34:90-93 reactions with bases, 9400 synthesis, M80-90, 93 with derivatives of metals and met- vanadium, 34.98 alloids, 9415-420 electronic structure retaining nitrogen, 9427 bond character, -69-70 in synthesis of p-methylene complexes, energy separation, 34:69 20164, 167-181 highest occupied molecular orbital Diazo compounds (HOMO), 34~69-70 photoreduction, 44.102 lowest unoccupied molecular orbital reactions with (LUMO), 3470 germenes and digermenes, 39294-295 molecular orbital (MO) calculations, metal carbonyls, 1012.5-129 3469 organocopper compounds, 12.290 Diazo group 96

Diazo group, from tosyl azides, 9399 Dibenzometallocins, 13212 Diazomalonate, reaction with germylene, 5-Dibenzometalloles, 13197-199, 203-205 M144-145 ring numbering system, 13197 Diazo-metal complexes, 10125 synthesis of fluorenc derivatives Diazomethane, 3E67.123 via dilithiobiphenyls, 13197 cycloaddition reaction with disilenes, by exchange reactions, 13204-205 39259 by metalloid insertion, 13205 reaction with by thermal ring closure, 13:204 acylmetalloids, 2123 2:3,5:6-Dibenzo-7,7,8,8-tetraphenyl-7,8- germcncs, 39294-295 disilabicyclo[2.2.2]octa-2,5-diene,327 hydrogen over metal surfaces, Dibenzyldimethylsiloxane, metal-catalyzed 20229-231 redistribution, 19245247 Diazonium organometallic syntheses, 104 Dibenzylideneacetone, reaction with palla- Diazonium salts dium atoms, 1572 carbonylation with nickel carbonyl, 29 Dibismaferrocenes, 39331 insertion into platinum hydrogen bonds, conformation, 39:339 13305 electrochemistry, 39344 a-Diazophosphines, nitrogen climination, molecular structure, 39333 44:180-181 Dibismuthinc Dibenzenechromium bonding theory, 3090 mass spectrum, 6290 chemical properties, 3081-82 neutron irradiation, 1k225 conformation, 39340 Dibenzheterocyclcs, 13196-221 diffuse reflectancc spectra, 3082-83 containing additional multiple bonds, absorption maxima, 3083 13213-216 red shift, 3082 anthraccne derivatives, 13206. nonthermochromic, 3080 213-13:215 Raman spectra, 3091 dibenzocycloheptatriene derivatives, similar compound, 3092-94 13215-2 16 diarsine, 3092-93 Group IIIB elements, 13198,200-201 dihalogen, 3093 Group IVB elements. 13198-201 diphosphine, 30:92-93 Group VB elements, 13199-201 structure, 3086-88 Group VIB elements, 13199-201 bond length, 30:87-88 nomenclature, 13196-197 synthesis, 3081 reactions, 13216-221 thermochromic, 3079 at carbon, 13218-221 ultraviolet spectra, 30:82 oxidation, 13220 1,2-Diboraatabenzcne,39385 ring cleavage, 1321Y 1,4-Diboracyclohexadiene metal complexes, substitution at heteroatom, 13216-218 35191-194 Dibenzodihydroborepins, 2272-273 Dibora-2,5-cyclohexadienes,39357, 384 2:3,5:6-Dibenzo-7,8-dimethyl-7,8-diphenyl-1,3-Diborafulvene metal complexes, 7,8-disilabicyclo[2.2.2]octa-2,5-dicnes, 35~205-208 327 Diboraheterocyclc metal complexes, ac- Dibenzometallepins, 13210-212 ceptor properties, 35187-188 Dibenzometallins, 13206-210 bifacial coordination, 35191 9,10-dihydroanthracene analogs, chromium complexes, 35188-189, 201, 13206-208 203 dihydrophenanthrene analogs, 13208-210 cobalt complexes, 35190-191, 193-194, of arsenic, 13209 198-204,207-208 of silicon, 13209 copper complcxes, 35203 97 1,2-Dicarbaclovododecaborane(1 2)

1,4-diboracyclohexadiene,35191-194 exchange reactions, 3274 nido carboranes, 35191-192 exchange with alkyl- and arylborons, synthesis, 35192-193 3266-267 X-ray structure analysis, 35193-194 hydrolysis, 3273 1,3-diborafulvene metal complexes, Lewis-base adducts, 3278-283 35205-208 oxidation, 3274 molecular structures, 35206-207 properties, 3:284-288 NMR signals, 35205 reaction, 3273-283 X ray structure analysis, 35205-207 as reducing agent, 1k3 9,10-dihydro-9,10-diboraanthracene, hydroboration, 1k12-14 35197-201 reduction of organoboron esters, 3270 bonding, 35197, 200 Diborane-borine equilibrium, 6206 molecular structures, 35199-200 Diborane(4) derivatives, 39373-374 NMR data, 35197,200 2,3-Diboratanaphthalene, 39385 reactions, 35197, 199, 201 Diboration reactions, 10251 X ray structures analysis, 35197, stereochemistry, 10254 199-200 1,4-Diborocyclohexadienes 1,4-dihydro-1,4-diboranaphthalene, from BF and alkynes, 18310 39194-197 complex formation, 18310-311 molecular structures analysis, 1,3-Diborolene 35195-197 complex formation, 18307-308 reactions, 35194-196 reaction with , X-ray structure analysis, 35195-197 18308-309 2,3-dihydro-1,3-diborolylmetal com- ring insertion of CO, 18307 plexes, 35202-204 Diborylacetylenes, 39366 EXAFS, 35204 Dibromosilacylclopentadiene, 3988 ligand properties, 35202, 204 Dibromosilole, 3988 reactions, 35203 1,2-Dibromo-1,1,2,2-tetrakis(2,4,6-triisopro- donor properties, 35187-188 pylphenyl) distannane, 38193, 199 iron complexes, 35189-192, 194-200, N-(Di-t-butoxysily)aniline, 39:189 202-208 1,2-Di-t-butyl-3-[bis(trimethylsilyl)] manganese complexes, 35187-188 methyl]l,2-diborirane, 39:378 nickel complexes, 35195-198, 200, Dibutylcyanocuprates, 3843 202-204 Di-t-butyldiazidosilane, photolysis, 39184 osmium complexes, 35189-191 1,2-Di-fert-butyl-l,2-dimesityldisilene, a-complex chemistry, 35188 39223,264 rhenium complexes, 35190 Di-t-butylfluorosilyl-2,6- rhodium complexes, 35190, 192,202,204, diisopropylpheylamine, 39180 207-208 Di-tert-butyl peroxide, laser photolysis, ruthenium complexes, 35188-189, 191 44:69-70 syn-facial coordination, 35189-190 3,5-Di-tert-butyl-1,2-o-quinone,39213 tantalum complexes, 35189-190 4,6-Di-terf-butyl-o-quinone,39215 vanadium complexes, 35188-189 Di-t-butylsilylene, 39166 zinc complexes, 35195, 203-204 (3,6)-1,2-Dicarbacanastide-metalcomplexes, Diborane, 3265290,39373 8:112-113 alcoholysis, 3273 Dicarba-closo-decaborane icosahedrons, alkyl and aryl derivatives, 3266-273 26:240 disproportionation, 3:274 1,5-Dicarbaclosopentaborane(5), 39956 equilibrium with borane, 3283 1,2-Dicarbaclovododecaborane(12), see ESR of radical anion, 15276 Carborane 98

1,7-Dicarbaclovododecaborane(l2),srr Neo- Dicarbonyls, Group 4B carborane ansa-titanoccne dicarbonyl derivatives, 2,4-Dicarhaclovoheptaboranes(7),3311, preparation, 25343-344 314 bis( q-cy1copentadienyl)dicarbon yl- Dicarbaclovohexaboranes(6), 3264, hafnium formation, 25336 30Y -31 1 bis( q-cylcopentadienyl) 1,5-Dicarbaclovopentaboranes(5), dicarbonyltitanium formation 3308-309 via other titanium complexes, 2,3-Dicarbahcxaborane(8), 3314-315 25331-333 Dicarbaundecaborane(13), 3315 by reductive carbonylation of Dicarbaundecaborane anion. reaction with Cp2TiC12/(Cp2TiC1)2,25322-324 thallium(1) acetate, 26355-256 via titanocene alkyl and aryl coni- Dicarbollide ions plexes, 25324-331 in aluminum n complexes, 26243-244 his( q-cylcopentadienyl) 1 in beryllium complcxes, t6.23 dicarbonylzirconium formation, boron complcxes, 26239-240 25333-336 n in complexes of Group VI elements, his( 7-indeny1)dicarbonyl complexes of Ti 26285 and Zr, preparation, 25342-343 in gallium complexes, 26:245-247 bis( q-pentametylcyclopentadienyl) in lead n complexes, 26:281 dicarbonylhafnium formation, reaction with Group VB element triha- 25341-342 lides, 26:283-284 bis( 7-pentametylcyclopentadienyl) in tin n complexes, 26:276-277 dicarbonyltitanium formation, n-1,2-Dicarbollyl (1,2-BsC2H,12-)complexes, 25336-338 891-100 his( q-pentametylcyclopentadienyl) cobalt, 8:97 copper and gold, 899 dicarbonylzirconium formation, Group VI metals, 8:Y1-94 25338-341 iron, 896 (q-C5Mes)CpM(C0)2 preparation, 25342 manganese carbonyl, 8:Y4 containing q-arenc rings, 25375-376 nickel and palladium, 8:98 containing one q5-CsH5ring, 25374-375 rhenium carhonyl, 894-95 containing n-bonded hydrocarbon chains, n-1,17-Dicarbollyl (1,7-B&H1 ,’-) com- 25372 plexes, 8100 functionally substituted v-cyclopentadi- Dicarbon bond enyl dicarbonyl complexes of Ti and formation and CxK, 28:105-106 Zr, preparation, 25345-346 scission and CJC, 28105-106 ‘H NMR, 25348-350 cis-Dicarbonylbis( 1,3-butadiene)tungsten, IR spectra, 25347-348 structure, 26313-314 mass spectra, 25351 Dicarbonylbis-(4‘-diene)metal complexes, photoelectron spectra, 25351 stercochemistry, 26311-313 physical properties, 25347 Di~arbonyl-(q~-‘~-1,3- structural properties, 25351 cyclohcptadienetrimethyl- Dicationic ethylene complex, 29175 phosphinechromium, structure, 26:318 Dichalcogenadistannetane, 39318 Dicarbonyl-( q4 “H-2,4-dimethyl-1,3- I,3-DichaIcogen-2,4-phosphasila- pentadienetrimethylphosphitechro- cyclohutane, 39211 mium, structure, 26:319 Dichloroboryl derivatives Dicarbonyl-q‘--(E,E)-2.4- from BzC14, 10:251-254,257-258 hexadiencbis(trimethy1phosphine) of ferrocene, 10263 chromium, structure, 26303 reactions with hydrides, 10267 99 Diene-metal complexes

Dichlorodigermane, dehalogenation, dimethyl derivative, preparation, 26232 M130-131 1,2,4,1’,4’-hexakis(trimethylsilyl)deriva- Dichlorodimesitylgermane, 39:293 tive, preparation, 26232 Dichlorodimesitylsilane, 326 ionization energies, 26235 Dichlorodiphenylsilane, 327 molecular orbitals, 26234-235 Dichlorodisilane, lithium action on, 38:27 synthesis, 26232 1,2-Dichlorodistannanes,38193 Dicyclopentadienyl metal compounds, Dichlorogermanes, 326 2:373-374 in digermene synthesis, M128 Dicyclopentadienyltin, 26268-274 Dichlorohexasilane, 32136 bond angles, 26270 Dichloroorganosilanes, 32164 bond lengths, 26270 1,l-Dichloro-l-silaethenes,39:148 ionization energies, 26:273 Dichlorosilane, 39:199 reactions, 26.268 reductive coupling of, 3834-35 with electrophiles, 26275 1,2-Dichloro-l,l,2,2-tetrakis[bis(trismethysi- with tin dihalides, 26274 lyl) methyl] distannane, 38194,199 synthesis, 26268-269 1.2-Dichloro-l,1,2,2-tetrakis(2,4,6-triisopro- Dicyclopentadienyltin complexes, pylphenyl)distannane, 38193 26:268-274 1,2-Dichloro-l,l,2,2-tetramethyldistannane, bond angles, 26270 38199,204 bond lengths, 26:270 Dicobalt heptacarbonyl, 4255-257 ionization energies, 26273 trans-Dicyanoethylene, 29:8-9 molecular orbitals, 26272-273 Dicyclopentadiene, manganesepentacar- reactions, 26274 bony1 alkyl reaction, 32200 Dicyclopentadienyltitanium dichloride, Dicyclopentadienylberyllium, 26226-228 2373 beryllium-carbon distance, 26:227 Diels-Alder addition, acetylenes to bor- dipolar nature, 26287 oles, 1674-75 substituent effects on structure, M144 Diels-Alder adducts, k18, 20,23 Dicyclopentadienylcalcium, 26237 Diels-Alder cyclization, 26132-133, 194 Dicyclopentadienyl complexes, mass spec- Diels-Alder cycloaddition, 35110 tra, 6285 Diels- Alder reactions zirconium chloride, fragmentation, 6287 in presence of nickel catalyst, 17:204 Dicyclopentadienylgennanium, 26258,262 retro, germene, 44A17-118 Dicyclopentadienylgermanium complexes Dienediones, synthesis, 4k221 bent germanocenes, molecular orbitals, Diene hydrosilation 26262 conjugated species, 17:441-443 bonding, 26:259-266 1,4-pentadiene, 17:418 bond lengths, 26258-260 Diene-iron bonding, k3 interplane angles, 26258-260 Diene-iron carbonyl complexes, k1-43 ionization energies, 26:273 acyclic dienes, 1:12, 18,33 molecular orbitals, 26:261-262,264, 273 conjugated complexes, k14-18 synthesis, 26258 conjugating ability, k9-10 Dicyclopentadienyllead, 26279-280 NMR studies, k12-13 gas-phase structure, 26279-280 nonconjugated complexes, k8-9,11 polymeric structure, 26:279-280 18-1 :20 synthesis, 26279 preparation, k13 Dicyclopentadienyllead complexes, 26273 structure, k2,4-10 Dicyclopentadienylmagnesium, 26232-235 X-ray studies, k4-10 decamethyl derivative, preparation, Diene-metal complexes, 3105 26:232 protonation, 8122-123 1,3-Diene-metal complexes 100

1,3-Dicne-metal complexes, "C NMR spec- electron, see Electron diffraction tra, 19273-278 X-ray, see X-ray diffraction Diene polymerization Difluorodirnesitylgerane, 39289 catalyzed by organolithium reagents, Difluoromethylidene complex 1855-97 bridging, 3k190 mcchanism terminal in nonpolar solvents, 18:71-78 cationic species, 3k189 in presence of polar ligands, geometry, 3k189 18:65-71 reactivity, 3k189-190 isomer distribution, 16:211 Digalloxane, 3941 via transition metal catalysts, 16:211 Digallylphosphine, 3928 Diene ruthenium(0) complexes, 29217-219 Digermaaziridine, 39295 Dienes 1,2-Digerniacyclobutadiene,reaction with allcnyl complexes from, 37:76-77 styrene, 44136 conjugated, hydroformylation, 17:44-46 1,2-Digermacyclobutane, 12 + 21 decomposi- hydrogenation to monoenes, 38171 -172 tion, 44:130 magnesium complexes, 26:233, 236 Digermadiene, synthesis, 39289 metallation, 26:127 1.2-Digermadioxetane, 39:301 in photochemical reactions of Group VI 1,3-Digermadioxetane, 39301-302 and VII metal carbonyls, 26:297-375 Digermaoxetane, 39:297 reactions Digermaoxiranes, 39302 addition to germenes, 39301 Digermenes, 2k272-273 with disilenes, 39257-258 cations in mass spectroscopy, 2k282-283 with organotin hydrides, k62-63 MO calculations, 2k280-281 with silenes, 39:111-118 physical properties, 44132-134 with tin doubly bonded compounds, preparation, 39:287, 290 39317-318 reactions, 39291, 294-295, 301 1,3-Dicnes reactions reactivity, 44134-138 with digermenes, 44136 synthesis, 44127-132 with germenes, M126-127 theoretical studies, M132-134 a-Dienyliron cations, 8146-150 Digermiranc, synthesis, 39295 cyclic systems, 0:146-149 Dihalocarbene complexes pentadienyl complexes, 8149-150 iridium Dienyliron tricarbonyls 13C NMR, 25175 cationic reaction in cyclic system, k30-31 IR spectroscopy, 25175-176 chemical reactions, k29 metallacycle formation, 25179-180 cis and (runs forms, 1:33 migratory insertion reactions, 25180 cyclopentadienc, k31-33 reactions with displacement of ligands, 1:28-29 electrophiles, 25180 preparation, k13 nucleophilcs, 23176-179 reaction with acyclic systems, k33-34 structure u- and n-bonded complexes, k33 carbene ligand orientation, 25175 Diethyl azodicarboxylate, reactions, with carbon-halogen bond, 25173 iridium compounds, 10135 metal-carbon bond, 25173 Diethyl ketone, synthesis by 0x0 reaction, trans influence, 25175 4258-259 synthesis Diethyl maleate, formation, 38182 cation generation for CCl?, com- Diethyl oxaloacetate. formation, 38182 plexes with silver salts, 25171 (2,6-Diethylphenyl)trichlorosilane,3215 CCI2 complexes from reaction of Diffraction L,M-CF, with BCI?, 2.5171 I01 Dihydridodecacarbonyltriosmium

CC1, complexes from reactions with nucleophiles, 25176-179 Hg(CCI,)z, 25170-171 structure conversion of CC12 complex to CFCl carbene ligand orientation, 25175 complex, 25171 carbon-halogen bond, 25173 modification of metal-carbon bond, 25173 dihalocarbene ligand-containing trans influence, 25175 complex, 25171 synthesis trihalomethyl derivatives, L,-CX3, cation generation for CCl, com- 25169-170 plexes with silver salts, 25171 osmium CCl complexes from oxidative addi- I3C NMR, 25175 tion of CC4to zero-valent Ru IR spectroscopy, 25175 complex, 25170 metallacycle formation, 25179-180 CC12 complexes from reaction of migratory insertion reactions, 25180 L,,M-CF3 with BC13, 25171 reactions with CCI2 complexes from reactions with electrophiles, 25180 Hg( CC13)2, 25170-171 nucleophiles, 25176-179 Dihalodisilane, 3821 structure 1,2-Dihalodisilanes, dehalogenation, carbene ligand orientation, 25175 39236-237 carbon-halogen bond, 25173 1,l’-Dihaloferrocenes, 32135 metal-carbon bond, 25173 Dihalogenocarbenes trans influence, 25175 carbene complexes from synthesis aryl lithium reaction, 25182 cation generation for CC12 com- formation mechanism, 29182-183 plexes with silver salts, 25171 reaction with carbenecarbonyl complexes, CCI2 complexes from reaction of 1420-21 L,M-CF3 with BC13, 25171 Dihalogermanium species, 37:152 CC12 complexes from reactions with 1,2-Dihalo-l,1,2,2,3,3,4,4-octa(t- Hg(CCl-j)Z,25170-171 butyl)tetrastannanes, 38207 conversion of CC12 complex to CFCl Dihalosilane, silyene-Lewis base complex complex, 25171 synthesis, 4334, 36 modification of Diheteroferrocenes, Group 15 elements, dihalocarbene ligand-containing 39325-326, 351 complex, 25171 conformation, 39339-342 trihalomethyl derivatives, L,-CX,, electrochemistry, 39343-344 25169-170 heterocymantrenes, 39333, 349-350 ruthenium molecular structure, 39333-339 I3C NMR, 25175 reactions, 39345-348 conversion of CCI, complex to CFCl spectroscopy, 39342-343 complex, 25171 synthesis, 39326-333 IR spectroscopy, 25175-176 Dihydridodecacarbonyltriosmium, 2649-55 metallacycle formation, 25179-180 bond angles, 2650 migratory insertion reactions, 25180 bonding orbitals, 265 modification of bond lengths, 265 dihalocarbene ligand containing com- bond orders, 265 plex, 25171 as catalyst, 2664-65 trihalomethyl derivatives, L,-CX,, NMR coupling, 2649-50 25169-170 synthesis, 2&49 reactions with vibrational spectra, 2650 electrophiles, 25180 Dihydridodecacarbonyltriosmium, reactions Dihydridodecacarbonyltriosmium 102

with alkynes, 2628 9,lo Dihydroanthracenylsodium-TMEDA, anion addition, 2652, 71 structure, 43275-276 with azobenzene, 2667 Dihydrobenzencs, 39:386 in carbon disulfide, 266, 18 Dihydrohoretes, 39379-380 carbonyl exchange, 2649, 51 Dihydrocarboranes, 3312-315 with CH2N2,26:24, 56-51 9J0-Dihydro-9 ,lo-dihoraanthracene metal with cyclohexadiene, 2635 complexes, 351977201 with cyclonona-l.2-diene, 2635, 66 1,4-Dihydro-1,4-diboranaphthalenemetal decarbonylation, 2651 complexes, 35194-197 with dialkyltin, 2k70 Dihydrodiboretes, 39579-380 with diborane, 2624 2.3-Dihydro-1,3-dihorolylmetal conlplexes, with diphenylacetylene, 26:62-63 35202-204 with electrophiles, 2652-53 5,10-Dihydro-5,10-dimethylarsanthrenedi- with ethylene, 2651 bromide, structure, 4208 to form mixed-metal triosmium clusters. 1,2-Dihydrodisilane, 39237 2671-76 Dihydrofuran-2-ylidene complexes, synthe- hydride exchange, 2651 sis, 41:212 in D20,26:4Y Dihydrogen, 32122 insertion rcactions, 2653-55 Dihydrogen complexes with alkenes, 2653-55 dissociation, 28:313 with alkynes, 2613, 18, 20, 53 ligands, 28301-317 with allene, 2618 discovery, 28301-302 with azides, M:53 IR spectroscopy, 28303 of carhonyl groups, a18 presence and TI criterion, 28:307-310 with diazo compounds, 2653 reactivity pattern, 28313 with imines, 2654 stereochemistry of, 28312 with isocyanates, 2653 structural data, 28302-303 with isocyanides, 2618 with isonitriles, 2653 NMR spectroscopy, 28:303, 306-307 nonclassical hydrides, 28310-313 with ketene, a18, 53 of ligand fragments, 26.54 physical data, 28304-305 mechanism, 2653 solid-state NMR spectroscopy, 28:310, with nitriles, 2653 312 with Ph,C==S, 2653 1,2-Dihydrophosphetes with sulfur dioxide, 26:18 fusion to 1,3-~yclohexadienering, 4k27 with terminal alkyncs, 26.27 synthesis with of a#-unsaturated esters and ketones, phosphaalkcnes, 4k10-11, 15-16, 25 2654 phosphaalkynes, 4k3Y-41 with nucleophiles, 2650-52 Dihydrophosphetylketene complex, synthe- photolysis, 2652 sis with phosphaalkynes, 4k36-37 reduction, 2652 1,4-Dihydrophosphinines,synthesis with in strong acids, 2652 phosphaalkenes, 4k26 with sulfur dioxide, 2652-53 Dihydropyridinyl carbene complexes, syn- in trifluoroacetic acid, 2652 thesis of binuclear compounds, 41:208 with trifluoromethyl cyanide, 26:27 1,2-Dihydropyridin-2-ylidene,synthesis, with triphenylsilane, M69 41:175 with unsaturated ligands, 2672-73 1,4-Dihydro-4-pyridinylidenecomplexes, Dihydrido ruthenium derivatives, 29179 synthesis, 41:204 Y ,lo-Dihydroanthracenylsodium-PMDTA, Dihydropyrrolylidene complexes, synthesis, structure, 43274-276 41:220 103 Dimetallatetrahedranes

2,5-Dihydro-l,2-selenaphosphole.synthesis gem-Dilithiooligosilane, 3831 with phosphaalkenes, 4k19 1,5-Dilithiopentasilane, 3832 P-Dihydrosilylation, 3844 Dilithiophosphide, 39289 2,5-Dihydro-l,2-thiaphosphole,synthesis 1,l-Dilithio-silacyclopentadienes, 3825 with phosphaalkenes, 4k19 1,4-Dilithio-1,2,3,4-tetraphenylbutadiene, a-Diimines, see 1,4-Diaza-1,3-hutadiene li- 39332 gands Dimerization Diindenylmagnesium, 26233. 236 catalyzed by GIC, 28:107-109 1,2-Diiodo-1,2-diphosphete,synthesis with germenes, 44:123-124 phosphaalkynes, 4k50 head-to-head, silenes, 39106-111 Diiodomethylarsine, structure, 4203 head-to-tail 1,2-Diiodo-l,l,2,2-tetra(t-hutyl)distannane, iminosilanes, 39176-178 38207 silenes, 39105-106 Diiron bridging complexes, 37:67-68, 250 ketenes, 282 Diisobutylaluminum hydride, 38205-206 organocopper compounds, l2:254-259 1,6-Diisocyanohexane, 39217-218,225-226 organometallics by copper(I1) salts, Diisopropylphenyl compound, synthesis, 12313 44:5 phosphinic acid, 4442-43 (2,6-Diisopropylphenyl)trichlorogermane, silenes, 2523-26 3226-27 tin doubly bonded compounds, 39314 (2,6-Diisopropylphenyl)trichlorosilane, Dimesitylfluorenylidenegermane, 39296, 3224 300 (2,6-Diisopropylphenyl)triethoxygermane, Dimesitylgermanimine, 39291, 293 3226 Dimesitylgermylene, 39:294 P-Diketonate derivatives, of organoplati- Dimesitylneopentylgermene, 39289 num(IV), 27:145-148 Dimesitylsilylene, 39:131, 176, 237 P-Diketone complexes of titanium(III), 2,2-Dimesityl-1-(2,4,6- 9144, 150-151 triisopropylphenyl)germaphosphene, his(cyclopentadienyl)titanium, 9164 39289 Diketones, reaction with digermenes, (Dimesityl)( tnmethylsilyl)silylazide, a137 39160-161 P-Diketones Dimetal compound fromation, 35157-172 interligand C-C coupling reactions, protonation of distinct alkylidyne-metal 2960-70 complexes, 35157-164 metalla-P-diketonates, 2547-48 protonations with HBF,Et,O, 33165-172 metalla-P-diketonato, 2549-55 1,4-Dimetalla-2-butanones, 32228 metalla-P-diketones, 2548-49 Dimetallacyclohutadienes, 2697-124 metalla-P-ketoimines, 2556-60 bond distances, 26100 triacylrhenato complexes, 2555-56 electronic structure, 26900-102 P-Diketones energy diagram, 26:lOl interligand C-C coupling reactions, molecular orbitals, 26101 2560-70 substitution of n-donor alkoxide ligands, metalla-P-diketonates, 2547-48 26102 metalla-P-diketonato, 2549-55 Dimetallacyclobutenes, 39299 metalla-0-diketones, 2548-49 Dimetallacyclopentane, 32118 metalla-P-ketoimines, 2556-60 Dimetallacyclopentene, 37:117 triacylrhenato complexes, 2555-56 Dimetallapolyyne complexes, 38:85, 109 1,4-Dilithio-1,3-butadiene,39328 Dimetallatetrahedranes, 2698-100 Dilithiohexadiene(TMEDA)>, 26220 conversion to ditungstacyclohutadiene, 1,4-Dilithiooctaphenyltetrasilane,3832 2699-100 Dimetalloalkanes 104

Dinietalloalkanes, 37:228 chemical reactions with chromium car- Dimetalloalkenes, 32228 bonyl complexes, 26316 1,3-DimetalloalIyl cluster compounds, 37:77 Dimethyl(cyclopentadieny1) aluminum, Dimctallocycle. 32238 26242-243 Dimethoxyethane, interaction with graphite in gas phase, 26243 intercalation compounds, 2897-98 in solid state, 26242-243 a,pDimcthoxypermethylpolysilanes. 3837 3,3-Dimethylcyclopcntyne, zirconocene com- 1,l-Dimethylallene, reaction with decacar- plex, 42187-189 bonyldimanganese, 26:362 Dimethyldiazidosilane, silyene-Lewis base 1-Dimethylaminobut-2-yne, 3278 complex synthesis, 4327 dodecacarbonyl triruthenium reaction, 5,S-Dimethyldibenzosilole,3825 3280 1,2-Dimethyl-4,S-divinylcyclohexene,fk63 Dimethylamino-group, stabilizing effect on 1,3-Dimethyl either p-t-butyl calix[4]arenc, arylcopper complexes, 12:235-237 structure of disodium salt, 43340-341 (Dimethy1amino)methylferrocene. 32157 5,6-Dimethylenebicyclo[2.2.1]heptene-2, 1-(4-DimethyIamino)phenyl-2,2- metal carbonyl complexes, 364 dicyanoethene, nonlinear optics, 42344 2,2-Dimethylethenyl radical, reaction with 2-DimethyIaminoprop-l-yne,3277-78 Sn hydrides, U94 (Dimethylamino) trimethylstannane, 1,l’-Dimethylferrocene, 32164 [Z 38215-21 6 Dimethylgermene, + 21 cycloreversion, U116-117 N,N-Dimethylanthranilamide, 39291, 293 Dimethylketene, decarbonylation of, 2814 2,S-Dimethylarsacymantrene, 39333. 345 Dimethylmercury 2,S-Dimethylarsaferrocene,39332 biological effects, 1325-27 Dimethylbenzosilacyclobutane, 39142 compound formation from organocobalt Dimcthylberyllium, 9196, 200-201 complexes, 11:421 structure, 9197 poisonous effects, 1322 2,S-Dimethylbismacymantrene, 39333 2.4-Dimethyl-l,.?-pentadiene,in photochemi- 2,3-Dimethylbutadiene, reactions cal reactions with metal carbonyl com- addition to germenes, 39301 plexes of chromium, 26316 with iminosilanes, 39173 with decacarbonyldimanganese, with tin doubly bonded compounds, 26354-358 39:317-318 2,5-Dimethyl-l-phenylarsole,39:332 2,3-Dimethyl-l,3-butadiene,photoreactions 1,1-Dimethyl-2-phenylcyclobut-3-ene, with tricarbonylmetal complexes 39149 of chromium, 26325-326, 328-329 3,4-Dimethyl-l-phenylheterole,39332 of molybdenum, 26345, 347 1,l-Dimethyl-2-phenyl-l-sila~yclobut-2-ene, of tungsten, 26341, 351 photolysis, 3984 Dimethylcadmium, comparison with lithiodi- 3,4-Dimethylphosphacymantrene, 39349 methylcuprate, U:279-283 Dimethyl (1-propynyl)aluminum, 26241-242 Dimethyl , B.185 Dimethylpropynylindium Dimethylcyanoarsine, structure, 4202 structure, 26249 4,5-Dimethyl-l,4,7-~yclodecatriene,synthe- synthesis, 26248 sis from butadiene and butyne, 863-67 Dimethylruthenium(I1) Complexes, 29173 Cope rearrangement to dimethyldivinyl- 1,l -Dimethyl-1-silabutadiene, 39149 cyclohexane, 863 1,l-Dimethyl-1-silacyclobutane,thermolysis, 1,5-Dimethyl-1,3-cyclohexadiene,in photo- 3972 chemical reactions with chromium car- l,l-Dimethyl-l-silacyclobut-2-ene,39:149 bonyl complexes, 26316 l,l-Dimethyl-2-silacyclopentene,39139 5,S-Dimethyl-1,3-cyclohexadiene,in photo- 1,l-Dimetliyl-3-silacyclop~ntene,39:139 Dioxygen

Dimethylsilene, 39100, 131 dicyclopentadienyltitanium, 196, 8, 18, from alkoxypolysilanes, 634 20-31 1,l-Dimethylsilene, 39148 permethyl derivative, 1913 Dimethylsilylene dicyclopentadienylzirconium alkyls, 1922 addition to diphenylacetylene, 1969-70 end-on bonded, 19108 insertion into Si-0 bond, 1960 by matrix isolation methods, 1564 and 1-methylsilene, interconversion, 2536 nickel, 19159 via photolysis of polysilanes, 1954-56 side-on bonded, 19:104- 108 stereochemistry, 1959 as olefin hydrogenation catalysts, 12331, reaction with 334 organic carbonyls, 1973 pentammineruthenium dication, 1919 silene, 39:138-139 reviews, 10344 2,5-Dimethylstibacymantrene, 39333 ruthenium, 16272 Dimethyl sulfoxide, as oxidant, 2103 titanium, 16272-275 1,2-Dimethyltetrakis (2,4,6-triisopropylphe- Dinuclear metal carbonyls, molecular re- nyl) distannane, 38199 arrangements, 16323-326 1,2-Dimethyl-l,1,2,2-tetrakis(2,4,6-triisopro- mechanisms, 16326 pylphenyl) distannane, 38194 and metal-metal bond strength, -Dimethyl-2,3,4,5-tetraphenylstannole, 1,l 16325-326 39380 Dinuclear metal complex Dimethyltin dihalides, 149-72, 84-90 bridgmg M-H-C, 30183 electron diffraction studies, 1471 bridging M-H-Si, 30174-180 molecular complexes, 1484-90 isoelectronic, 30:204-207 with triorganostibine sulfides, rhenium, 30179 14195-196 tungsten, 30178-179 Mossbauer studies, 1472 Diolefin complexes, conjugated, structures, NQR studies, 1472 5100-105 X-ray diffraction studies, 1471-72 2,6-Dimethyl-2-vinyl-1,3-dioxa-6-aza-2- Diolefin-metal complexes, 354-63 DIOP(2,3-o-isopropylidene-2,3-dihydroxy- silacyclooctane, hydrostannylation, 43202 1,4-bis(dipheny1phosphino)butane) Dinegative ions, of aromatic hydrocarbons, preparation, 12339 2118-119 use in asymmetric synthesis electronic absorption spectra, 2132-140, rhodium complexes, 12339-345, 145-152 35 2 -3 5 5 singlet ground states, 2143-144 ruthenium complexes, 17356-357 triplet ground state, 2142 supported on polymers, 17366-367 Dinitrobenzoate esters, of pentadienylmetal Diorganotin bisamides, 38205, 221 complexes, 26145 Diorganotin dichloride, 38193 Dinitrogen Diorganotin dihydrides, 38205, 221 activation by transition metal complexes, 1,3,2-Dioxaborolanes, alkyl exchange, 2260 16271 2,4,1,3-Dioxadisiletane,39:224 end-on and side-on bonding, 16271 Dioxazadisilolidine, 39261 reduction 1,2-Dioxetane, 3&264-265 catalytic systems, 19:34-36 1,3-Dioxetane, 3&265-266 dicyclopentadienyls and Grignard re- Dioxygen agents, 196, 18 end-on vs. side-on coordination, via titanium compounds, 1918-20 16274-275 Dinitrogen complexes insertion into metalcarbon bonds, chromium carbonyls, 1812 n74-75 Dioxygen 106

insertion reactions with cobaloxime com- q':$-1,3-Diphosphacyclobutenyl complex, plexes, 1k430-431 synthesis with phosphaalkynes, 4k38 iron complexes, 16:274 Diphosphaferrocene, 39328 titanium complex, 16274-275 conformation, 39:339, 341 2,4-Dioxy-l -metalla-l,3-butadienes, synthe- electrochemistry, 39344 sis, 4k215-216 molecular structure, 39:333 a, cp-Dipenylpermethylpolysilane, 38:35 reactions, 39347 Diphenylalkylstannaiies, reaction with Sn 1,2-Diphosphaferrocene, synthesis with pho- hydrides, &99 sphaalkenes, 4k6, 8, 20 1.3-Diphenylallyllithium,diethyl ether ad- Diphosphasilaallyl salt, 39200 duct, 26218-219 2,3,1-Diphosphasilabut,l,3-diene,39:220 Diphenylcyclopropenone, reaction with ke- Diphosphenes, 21:271-272 tenes, 28:14-15 synthesis and characterization, 44:44-45 Diphenyldiazomethane, 39216 (cot)(v4-l ,3-Diphosphete)hafnium, synthesis reactions with phosphaalkynes, 4k47 with arsasilenes, 39224-225 Diphosphides, multiple bonding, 3926-27, with germenes, 39294 35,37 Diphcnyldiazomethane, reactions with 1,3- qh-1,3-Diphosphinine, synthesis with phos- ditungstacyclobutadiene, 26119 phaalkynes, 4k45 Diphenyldichlorosilane, 37:137 Di(phosphino)carbenes Diphenyldikctone, reaction with phosphasi- reactivity, a203 lene, 39214-215 theoretical studies, a179 1,2-Diphenyl-1,2-dimethyl-l.2- Diphosphinogermane, 39:289 dichlorodisilanc, 37:7 Diphosphirene complex, synthesis with pho- Diphenyldimethyhiloxane, metal-catalyzed sphaalkynes, 4k36 redistribution, 19:245-247 1,3-Diphospholide anion, phosphole synthe- Diphenyliodonium salts, 1&3 sis, 4k32 Diphenylketene, 28:13, 16 Diplatinum centers, chemistry reaction with PhMgBr, 23 dppc bridged complexes, 3532-35 1,5-Diphenylpentadienyllithium,26:129 bond distances, 3533-34 2,6-Diphenylphenol, synthesis, 4450 elimination, 3534-35 Diphenyl(phenylethynyl)aluminum, molecular structures, 3532-34 26241-242 NMR characterization, 3532 bonding, 26:241-242 reactions, 3532-35 Diphenyl(phenylethyny1)bordnepyrdine. dppm bridged complexes, 3511-32 39378 A frame compounds, 3515-19.21-24 Diphenylphosphide, 38164 bond distances. 3514, 20-23 (2-Diphenylphosphinoethyl) trimethylam- CzH4 elimination, 3529 monium cation, 38179 coupling constants, 3523 1, n-Diphenylpolyenes, spectra, 2136-137 geometry, 35:12,22 2,3-Diphenylyuinoxaline. structures of so- Hz elimination mechanism, 3326 dium and potassium salts, 4x328 intermediates, 3517 Diphenylsilane, disproportionation, 7:39 inversion, 3519 1,2-Diphenyltetrarnethyldisilane,3&37 molecular structures, 3511, 13-14, Diphenyltin, 38218 19-20 Diphenyltitanium, %180 NMR spectrum, 3512.23-24 1,3-Diphosphabicyclo[l .l.O]butanediyl me- orbital bonding, 3522 tallocenes, synthesis with phosphaal- oxidative addition, 3529, 31 kynes, 41:51 palladium elimination reactions, 3529 1,3-DipIiosphacyclobutanes,39:214 photochemical decomposition, 3531 107 Disilene

PPh3 substitution mechanism, 3515 Direct Process Reaction, 3860, 67-69, preparation, 3512, 16, 19-20 74-75 reactions, 3525-27 Dirhodium complexes, 32255 structures, 3513 Diselenium monoxide, 36:171 thermodynamic favorability, 3518 Diselenoester, coordinated ligands, electro- water-gas shift reaction, 3527 philic addition to, 25135-138 X ray diffraction, 3514, 17 1,4-Disilabarralenes, 39150 dppm related complexes, 3513, 16, 18- 1,4-Disilabenzene, 39101, 106, 150 20, 22,26,29-31 Disilabenzenes, 39150-151 preparation, 3516, 19 Disilabicyclo[2.2.2]octadiene, cyclorever- structures, 3513, 19 sion, 39237 treatment, 3520 1,3-Disilacyclobutane-2,4-diirnines,39219 halide bridged complexes, 352-3 Disilacyclobutanes, 32133 reactions, 352-3 formation, 39:77, 104-105, 107, 142 Zeise’s dimer, 352 pyrolysis, 39:90-92 hydride bridged complexes, 35:3-5 silenes from, 39:73, 75 characterization, 354 1,2-Disilacyclobutenes, 1990-92 dppe syntheses, 354-5 1,4-Disila-2,5-cyclohexadiene,39:150 molecular structure, 354 Disilacyclohexadienes, 19227 preparation, 353-4 ring contraction via Fe(CO)3 derivative, product nuclearity sensitivity, 354 19:230 organic bridging group complexes, 355-7 Disilacyclopropane, 39130- 131, 259 preparation, 356-7 1,2-Disilacylcobutane, 3840 reactions, 355-7 Disiladioxetanes, 39214, 262 X-ray diffraction charaterization, 356 Disilagermirane, photolysis, 44:130 Zeise’s dimer treatment, 356 Disilane-bridged [2]ferrocenophanes, orthometalated phosphine ligand com- 32157, 163 plexes, 357-10 Disilanes, 382-4, 10-12, 18 coupling constants, 3510 alkyl disilanes, M29-130 dppe ligands, 358 aromatic, silenes from, 39128 molecular structures, 359 aryl hsilanes, k106, 109-110 reactions, 357-10 cleavage of Si-Si bond, k106-107 X-ray characterization, 358, 10 nomenclature, 1:93 platinum-platinum bond complexes, properties, 1:134 351-2,35 reactions, 1915, 136 Diplatinum p-phenylethenylidene complex, with organic halides, catalysis via 37:241 [Pd(PPh,),], 19:232-234 Dipole moments Disilanyl anions, 3826-28, 51-52 metal nitrosyl complexes, 2234 Disilanylene 1,2-dianion, 38:27 methyltin halides, 1468, 76 Disilanyllithium, 3811, 26-27, 40 transition metal alkyls (aryls), 2173-174 Disilanylpotassium, 3826 transition metal silyls, 11:288 Disilaoxiranes, 39261-262, 264 1,3-Dipoles, reaction with phosphinocar- 1,4-Disilapentane, synthesis by dehydrocou- benes, 44:199-200 pling, 42383 Dipyridyl complexes Disilatriazoles, synthesis, &31-33 Group VI carbonyls, 3200,208, 210 Disilazanes, 9316-318 halogenation, 3211 Disilene, 328, 3972, 159, 194, 232, 239 manganese, 3213 bridged, 39238 palladium, 3250 masked, 3838-39 Disilene 108

stability toward oxygen and heat, mixed derivatives, 38198-199 39:239-240 peralkyl derivatives, 38:195, 197-198 stable, 39234-235,269 peraryl derivatives, 38:194-197, 200 ionization potential, 39247-248 properties, 38199-203 molccular structure, 39244-247 reactivity, 38203-204 properties, 39239-240 structure, 38194-199 reactions, 39:248-269 synthesis, 38191-194 spectroscopy, 39240-243 Distannenes, 38232,39309 synthesis, 39:232-238 molecular structure, 39:3W Disilene adduct, 328 reactions, 39315,318 Disilene-metal complexes, 39:268-269 spectroscopy, 39:308 Disiloxane, 39131,171 Distibaferrocenes, 39:328, 331 redistribution and retention at silicon, conformation, 39339 19:243-244 electrochemistry, 39344 Disilylacylsilanes, photolysis, 3974,81-82 molecular structure, 39:333 Disilylaklenes, photolysis, 3979 reactions, 39:347 Disilylalkynes, photolysis, 3974,80 Distibine, 3077-95 Disilylaromatic compounds, photolysis, bonding theory, 3088-YO 3974,80 HOMO-LUMO gap, 3089-90 Disilylcarbenes, 3975 Huckel calculation, 30:88 Disilyldiazoalkanes, photolysis, 39:76 chemical properties, 3080-81 Disilyne, 3235-36 conformation, 39340 l,l-Disodio-2,3,4,5-tctraphenyl-l- diffuse reflectance spectra, 3082-83 siiacyclopentadiene, 38:24 absorption maxima, 30:83 Disodium acetylide, crystal lattice, 27:196 red shift, 3082 Displacement electron diffraction, 30:92 of ketene ligand, 2843-44 uonthermochromic, 3077-78 in synthesis of uucleophile-carbonyl ad- Raman spectra, 3090-91 ducts, %I48 "'Sb-Mossbauer spectra, M92 Displacement reactions similar compound, 3092-94 dialkylalkenylhoranes rearrangement, diarsine, 3092-93 2281 dihalogen, 30:93-94 trialkylboranes, and dienes, 2280 diphosphinc, 3092-93 trialkylboranes, and trialkenylboranes, ditelluride, 3094 2282 interpnictogen, 30:93 Disproportionation, in organosilicon chemis- structure, 3084-86 try, 19213-255 crystal packing, 30:85 Disproportionation reactions, alkoxypolysi- synthesis, 3080-81 lanes, 632 thermochromic, 3079 Dissociation, metal( 1oid)-metal(1oid) bonds, ultraviolet spectra, 30:82 236 Distortion enhancement of polarization Dissociation constants, ferrocenoic acids, transfer 10: 106 advantages, 23217 Dissociation energies, see Bond dissociation application to 2ySiNMR spectroscopy, encrgics 23198-208 Dissociative catalytic cycle, in ethykne hy- comparison with INEPT, 23206-208 droformylation, computer representa- methyl substituted polysilanes, 23198- tion, 26202-203 200,202 1,2-Distannacyclobut-3-ne,38232 signal enhancement, 23204-206, Distannanes, 38190-191,210 215-216 109 Dodecacarbonyltriosmium

silanes, 23:202-204 Diynes, reaction with organotin hydrides, siloxanes, 23199-202 k62-63 limitations, 2k217 1,4-Diynes, via propargyl halides and or- pulse sequences, 23196-197 ganocopper compounds, 12.266-267 theory, 23213-217 Dodecabenzylcyclohexastannane, 3&221, Distortionless enhancement by polarization 223 transfer, W.419 Dodecacarbonyltetrairidium, bond enthal- Disulfur monoxide pies, 2641 complex synthesis, 36167-169 Dodecacarbonyltriosmium, %1-3,39-49 coordination reactions, 36169-170 bond enthalpies, 2641 structural studies, 36170-171 bond order, 265 1,2-Dithiadistannetane, 38232, 39:318 as catalyst, 26:63-65 1,3-Dithiadistannetane, 39318 molecular symmetry, 26:39-41 1,3-Dithianes, hydrolysis, 2105 nuclearity, 2&41 Dithiaphosphadigerminane, [2 + 21 cyclore- changes in, 2665-68 version, &117 pysisorbed on oxide supports, as catalyst, Dithietene-metal complexes, mass spectra, 26:63 8217,220,226-227, 274 reactivity, 26:41-44 Dithiocarboxylate complexes, by carbon di- rotation of Os(CO), units, 2639 sulfide insertion reactions, 1274 spectroscopy, 2640-41 Dithioester, coordinated ligands, electro- structure, 2639-41 philic addition to, 25135-138 axial carbon atom distance, 2639 1,2-Ditolyl-l,1,2,2-tetrachlorodisilane,327 bond angles, 26:40 Ditropyl chromium tricarbonyl complexes, bond distances, 26:40 4356 a-electron density, 2639 1,3-Ditungstacyclobutadienes,26:97-124 equatorial carbonyl ligands, 26:39 bonding orbitals, 26:lOl-102, 104-105 synthesis, 2639-41 Fenske-Hall calculations, 26100-102 Dodecacarbonyltriosmium, reactions paramagnetism, 26:104 acetic acid, 26:66 photoelectron spectra, 26103 acetylenic phosphine, 2611 reactions acid halides, 26:13 with alkynes, 26105-111 alkenes, 2628 mechanism, 26107-111 alkynes, 2631, 34 rate, %lo9 amino groups, 26:27, 43 with allenes, 26:111-115 benzene, 2630 syn-anti isomerization, 26114-115 carbon monoxide, 2641-42,64 mechanism, 26113-115 dimethylaniline, 2624 reaction rates, 26113 dimethyl phenyl arsenide, 2612 stereoselectivity, 26113-115 diphenylacetylene, 26:23, 61 -62 with diphenyldiazomethane, 26119 1,2-disubstituted alkenes, 26:28 halogenation, 26:102-103 electrophilic addition, 2642 with isocyanide and carbon monoxide elemental sulfur, selenium, or tellurium, ligands, 26116-118 26:12,67 1,2-Divinylcyclobutane, &56-59 ethylene, 26:24, 27 Cope rearrangement, 856-57 halogenation, 26:7, 24, 66 cis-l,2-Divinylcyclohexane,863 in high-boiling polar solvents, 2642 Divinyl ketones, byproducts of carbonyla- hydride addition, 2643 tion, 25 hydrogenation, 2642-43 Divinyl mercury, 3:35 indene, 2629 Divinylsilene, 39145 isocyanides, 26:45 Dodecacarbonyltriosrniurn 110

Me3N0, 2643, 45 Dodecamethylcyclosilane, silyene-Lewis methyl acrylate, 26:42, 66 base complex synthesis, 4327 met hyllithium, 26:19 Dodecamethylsilane, silyene-Lcwis base methyl phenyl sulfide, 2k12 complex synthesis, 4319. 22 monodentate ligands, 2613 Dodecamethylsilicoccne, 39238 (S)-(~)-nicotine,2623 Dodecaphenylcyclohexastannane, 38218, nucleophilic attack at CO, 2613, 43 222 PhCH,NH2,2618-19 Dodecarbonlytriiron, bond enthalpies, 264 I phenyl azide, 26:10 Donor-acceptor model, 39:4 in (+)-1-phenylethylamine, 2622 ~-DOPA(3,4-dihydroxyphenylalanine),syn- photolysis, 26:65-66 thesis. 12340 PHZPh,2627 Doppelkegel structure, k240-241, see also protonation in sulfuric acid, 2642 Sandwich structure pyridine, 26:66 Dotz reaction, in alkyne annulation, pyrrole, 2629 44:278-287 reduction, 26:43, 66 dppc bridged complexes, 3532-35 in refluxing octane, 2667 dppm bridged complexes, 3511-32 S(NSiMe3)2,2613 dppm related complexes, 3513, 16, 18- 20-35:22,26,29%31 sodium horohydride, 2643 Duroquinone, nickel-olefin complex, tertiary phosphines or arsines, 2644 218-21 thermal decomposition, 26:42 Duroquinone complexes, 5: I24 trichlorosilane, %69 Dyotropic rearrangements, 1633-63 trimethylsilane, 26:68-69 of ally1 silylmcthyl ethers, 1647-52 triphenylphosphine, 2637 of 1,2-his(silyl)derivatives, 1635-47 vacuum pyrolysis, 2642, 66-68 orbital symmetry considerations, 1635 Dodecacarbonyltriosmiuni substitution com- as pericyclic valence isomerizations, pounds, 2644-49 1633-34 alkenes, 2645 as catalysts, 26:63-65 dienes, 26:45 E dynamic behavior, 21c.45-49 intraniolecular behavior, 2647-49 [EzCo4(C0)11]’~’2-.structure and bonding factors, 4225-26 ligand chemistry, 2655-65 [E2C04(CO),,]”-,structure and bonding fac- spectroscopy, 2645, 47 tors, 4255 structure, 2645-49 Effective atomic number, k177 diencs, 2646-47 Effective atomic number rule, 3182. organic cyanides and isocyanides, 26:46 1317-18 synthesis, 2644-45 Eighteen-electron rule. 1513-14 tertiary phosphines, 26:45-47 Electric-field-induced second harmonic. Dodccacarbonyltriruthenium, 3258, 81 mcasuremcnt of organometallic sec- bond enthalpies, 2641 ond-order nonlinear optical properties, 3 -dirnethylaminobut-2-yne reaction, 3%80 42304-305 2,4-hexadicne reaction, 3176 Electrocatalytic reduction, carbon dioxide, substitution reactions. 2644 22156-157 Dodecamethylcyclohexasilanc, 3826, 32, Electrocatalyzcd substitution of organomc- 34-36 tallics, 24:104-105-24108-24110, 1 16, “Si NMR spectrum, 23198 118,122 Dodecamcthylcyclohexastannane, 38221, optimum conditions, a116 228 stereospccificity, 24109-110 111 Electronic spectra

Electrochemical potentials, metal-alkynyl carbon-bridged, 15239-247 complexes, 3889-90 hydrogen-bridged, 15247-249 Electrochemical reduction, of areneiron beryllium, 15245 complexes. 1399 structures, 15251-254 Electrochemical studies theoretical studies, 15255 borinatometal complexes, 18319-320 bonding, 15236-239 cobalt complex, 31:226-228 with bridges between unlike metal atoms, ESR of radical anion, 3k227-228 15262-266 rearrangement rate of radical anion, Group 11-Group 111 compounds, 3k228 15262-263 cycloocta-1,3,5,7-tetraenecomplex, lithium-Group I1 compounds, 31:226-227 15265-266 octafluorocycloocta-l,3,5,7-tetraenecom- lithium-Group 111 compounds, plex, 3k227 15263-265 triple-decker sandwich complexes, 18328, gallium, 15244,250-251 330-331 Group I1 derivatives, 15:251-255 Electrochemical synthesis indium, 15244,250-251 cationic metal carbonyls, 8:129 lithium, 15255-262 organometallic compounds, 6:15 bonding, 15260-262 Electrochemistry degree of aggregation, 15255-258 d4 alkyne complexes, 29:69-71 structures, 15258-260 diarsaferrocenes, 39343-344 magnesium, 15255-256 isocyanides, 22255 structures, 15255-256 octafluorocycloocta-1,3,5,7-tetraenederiv- structures, 15235-268 ative cobalt complex, pentamethyl- transition metal derivatives, 15266-268 cyclopentadienyl, 3k226-228 Electron-deficient ~~-dienechromiumcom- Ru~C(CO) 15,4348-49 plexes, 26:315-325 transition metal clusters, 3325-26 Electron diffraction Electrolytic preparation, tetraalkyl leads, gas-phase, see Gas-phase electron dif- 2246 fraction Electron affinities, conjugated hydrocar- manganesepentacarbonyl alkyls, bons, 2120-123 32177-178 Electron counting organoarsenic compounds, 4210-212 carborane, 30100-101 organosilicon pseudohalides, 5192 cluster, 30:218-219 silicon-sulfur compounds, 539 in dicarbollylboron complexes, Electron diffraction studies, 1467, 69, 26:239-240 71-72 heterocarborane, 30101, 136-137 on trimethylaluminum, 15241 isoelectronic compound, 30190-192 Electron donor power in transition metal chemistry, computers of cymantrenyl group, 10110 and, 26A70-171 of ferrocenyl group, 10107 in triosmium clusters, 26:4, 79 (+ values for metallocenyl groups, 10109 Wade’s rules, 30136 Electronegativity, relation to chemical shift, Electron deficiency, 3365-366 316 Electron deficient bonding, in beryllium Electroneutrality principle, l512 complexes, 9197, 251, 253 Electronic effect, &Me5 group, 6:72 Electron-deficient bridge-bonded main Electronic spectra group compounds, 15235-268 acylmetalloid compounds, R114 aluminum, 15239-250 n-ally1 complexes, 8108-109 bonding, 15237, 249-250 d4 alkyne complexes, 2964-68 Electronic spectra 112

@-ketometalloids,2147 silaphenalene, 15296-297 metal carbonyl clusters, 18246 silicon-nitrogen compounds, 15310 metal nitrosyl complexcs, 2233 substituted arenes, l5285-291 and MO calculations, E6-9 triarylborons, 13276 organosilicon compounds, 7:41-43 cesium benzenide, 16:200 transition metal alkyls (aryls), 7:171- 172 cluster radical ions, 22172 Electronic spectroscopy detection of radicals in thermal re- alkynyl-metal complexes, 3884-88 arrangement of benzyl silylmethyl polystannancs, 38199-202,210-212 ethers, 16:53-54 Electron impact, bond dissociation energy 1,4-diaza-1,3-butadiene radicals, 21:2 13 values, 253-54 metal complexes, 21:213-217 Electron impact fragmentation, see Mass dicyclopentadienyltitanium compounds of spectra bipyridyl, 19:39 Electron paramagnetic resonance of dihydride anion in nitrogen fixation, on bisarene complexes, 1354 1919 iron, 1393-94 metal nitrosyl complexes, 2234 vanadium, 1359 nonacarbonyltricobaltcarbon anion, digermenes, 44:133-134 15313 Electron radicals, see Nineteen-electron or- olefin complexes, 1559 ganometallic radicals; Seventeen-elcc- organometallic nitroxide radicals, tron organometallic radicals 169 7- 18 Electron spectroscopy for chemical analysis phosphine methylcnes, 9298 measurement of electron density in plati- and photochemistry of organometallic num complexes, 1444 alkyls oletin complexes, 1520 chromium, U264 olefin-nickel complexes, 19268 molybdenum, 24265 polymer-supported catalysts, 12263 titanium, 24257-258, 260, 263,265 of ylide gold complexes, 2097 uranium, 24254 ionization potentials, 2099 vitamin BIZmodels, 24304-305 Electron spin resonance zirconium, 24260, 265-266, 268 cobalt isocyanide complexes, 11:64 polymer-supported niobium complex, kinetic ESR, a71 15 194 organoarsenic compounds, 4223 polynuclear organometallics, a92-97, organometallic radicals, 14:346-391 9Y-100, 102, 104, 106, 113 polymer-supported rhodium catalyst, silyltetrazene radical cation, a234 12364 transition metal alkyls(ary1s). 2173 steady-state ESR. &71 trivalcnt organo-Group IVB radicals, Electron spin resonance spectra 19:139, 142 anion radicals Elcctron spin resonance spectroscopy, and acylsilanes, 15310 thermolysis of bis(trimethylsily1)dia- benzheterocycles. 15291, 295-296 zene, 23146-147 from bis(trimcthy1)silylethene and ace- chromium, 235, 8, 13. 17-18, 64, 68 tyltrimethylsilane, 2138 cobalt, 2328, 57-58,60-62 diborane, 15276 iron, 2324-28,36, 53,71, 73-74 Group I compounds, 15275 manganese, 2318-19,38, 51 Group IV compounds, 15277-282 molybdenum, 23:13, 18, 48 naphthalene derivatives, 15291 nickel, 2333, 62 polyphenylenes, 15291 rhodium, 2341, 60 polysilancs, 13305-307 ruthenium, 2327 silaacenaphthene, 15296-297 titanium, 2342-44 113 Elimination reactions

tungsten, 2313, 18,48-49 with transition metal carbynes, 2778-82 vanadium, 2367 with trimethylenemethane metal com- Electron transfer, in organomagnesium re- plexes, 27294-295 arrangements, 16149-150 Electrophilic additions Electron-transfer reactions to carbene complexes, 25127 borabenzene metal complexes, to carbyne coniplexes, 25133 25223-225 to coordinated imidoyl acyl, thiocyl, di- in cobalt(I1) complexes, 11:389 thioester, and diselenosester ligands, organotransition metal complexes, 25135-138 231-93 reactions of mediation by CO, 23:292-296 dRalkylidene complexes of Ru, Os, Electron-transfer reactions, polynuclear or- and Ir, 25164-167 ganometallics, X87-130 chacloformaldehyde complexes, bridged bimetallics, 2498-110 25166-167 clusters, 24111-122 gold adducts, 25166 effect of capping ligands, 24113-114, with halogens, 23167 119, 123-124 sulfene complexes, 23166 electrocatalytic substitution, X104- borabenzene metal complexes, 25230 105, 108-110, 116, 118, 122 dihalo- and monohalocarbene com- and MO calculations, %loo, 104, 107- plexes of Ir, Os, and Ru with, 108,113, 115, 118-120 25180 redox induced rearrangements, 24:ll. 94, 0s and Ru carbyne complexes with 97, 99-101, 105-106, 116-117, Group I metal halides, 25191 119-122 halogens, 25192 cubane clusters, 24114-116, 119 protic acids, 25190 cyclopentadienylcobalt complexes, sulfur dioxide, 25191 24:106- 107 Electrophilic behavior sandwich complexes, 2489-95 of coordinated ketenes, %51-54 triple deckers, U95-98 of ketenylidene complexes, 28:73-74 Electron-withdrawing effects, of chromium Electrophilic cleavage series, k170, 205 tricarbonyl group, 1355-56 Electrophilic substitution, on arenechro- Electrophiles, reactions of mium tricarbonyl compounds, 1385 abstration reactions, computer representa- Electrophilic substitution reactions tion, 26193 in ferrocenes, 1039, 81 addition reactions orienting effect of ferrocenyl group, 1040 to carbene or carbyne, 26:193 stereochemistry, 1025 computer representation, 26193 Element-element bond to unsaturated bonds, 26193 dehydrocoupling, see Dehydrocoupling with anionic transition metal hydrides, synthetic routes, 42363-364 27:30-34 Elimination, of sulfur dioxide from metal with dihydridodecacarbonyltriosmium, sulfinates, 12:36-37 2652-53 a&Elimination, from P-halogenomethy- formation of pentadienyl compounds, lene phosphoranes, 44:181-182 26136 P-Elimination, with nucleophile-carbonyl ad- to form cyclopentadienyltin cations, ducts, 28179-180 26275 Elimination reactions with isonitrile and thiocarbonyl ligands, of ally1 silanes, 27285-287 27:63-64 computer representation, 26177-178, with pentadienylmetal complexes, 189-190 26131-135 feasibility matrix, 26190 Elimination reactions 114

as source of transition metal alkyls (ar- in alkene polymerization, 24:143 yls), 7:166-167 hydride bridge, oligomer, 24145-147 1,2-Elimination reactions, in silene synthe- methyllithium derivative, 24595-396 sis, 2510 ESR, see Electron spin resonance Enamine, k222 a-Ester radical, reaction with Sn hydrides, telomerization with butadienc, 12159 44.96 4-Enamino-l-metalla-1,3-dienes.synthesis, Esters, reaction weith silenes, 39:126 4k208-209 Ethane, oxidation to alcohol, 38169-170 Enantiomers, optical resolution, 18153-160 Ethane-1,2-diolato(2-) bidentate ligand, Endoboron compounds, 2288 spirocyclic A%-silicates ENDOR, of silacyclopentadiene anion radi- NMR studies, 44:240 cals, 15279 synthesis, a239 Enc reactions X-ray diffraction studies, &239 germenes, 39:295-297 Ethanol, reactions with unsaturated germa- iminosilanes, 39172-173, 178 nium coupounds, 39291-292 silenes, 39:114, 117. 128-130 Ethene- t ,2-diolato(2-) bidentate ligand, in tin double bonded compounds, 39:315, spirocyclic hzSi-silicates 317 ab initio studies, U237-238 Energy NMR studies, 44:238-239 bond dissociation, Group 14 hydrides, synthesis, a236 U68-70 X-ray diffraction analysis, U236-237 ionization, germenes, MI21 Ethers, oxidation of, 38170 Enolate Ethoxy(1-alkyny1)carbcne complex, cobalt derivatives of alkali metal carbanions, complex, 4k227-228 22254-258 Ethoxycarbonyl cobalt complex, hydrogena- metal derivatives, 1017 tion of, 28.176-177 stereoisomerism, 1017 2-Ethoxy-l-metalla-1,3,S-hexatrienes Environmental hazards, methylmetal deriva- tives, 3871 cyclization reactions, 41:175 Enzymes, containing cobalt corrinoids pyridines via fragmentation, 4k176 isomerase reactions, 11:441 l-Ethyl-l-alumino-2,3-dicarba-closo- methyl transfer reactions, 1k439 dodecaborane Epimerization, of chiral metal complexes, rearrangement, 26:244 18:168 structure, 26244 cobalt, 18185-186 synthesis, 26243-244 equilibrium control by optically active li- tetrahydrofuranyl adduct, 26:244 gands, 18:188 , oxidation to alcohol, 38169 iron, 18:185 2-Ethyl- 1,3-butadiene, photochemical reac- molybdenum, 18:177-178 tions with carbonyl complexes Episulfides, reaction with disilenes, of chromium, 26298 39259-260 of molybdenum, 26:299 Epoxides, reaction with disilenes, 39:262 Ethylcobalamin EPR, see Electron paramagnetic resonance biosynthesis, 20326 u-n Equilibria in organocobalt complexes, and mercuric acetate, 20317 11:399 and stannous chloride, 20346 Erbium complexes Ethyl diazoacetate, reaction with molybde- alkyls, W.136-138 num complexes, 10126 his (cyclopentadienyl) derivatives Ethyldimethylamine, reaction with iminosi- bridged dimmer, 24:139-140, lane adducts, 39:179-180 143 Ethylene 115 Exchange reactions

catalyzed codimerization with butadiene, 8-Ethylenic metal complexes, 2329 17:269-318 Ethylidene-bridged complex, 3271 coordination, and reaction with ammo- Ethyllithium nia, 1829 mass spectrum, 3371-372 dimerization nickel-induced synthesis from hydrogen computer representation, 26195, and ethylene, 19:109-111 198-199 structure, 3369-370 proposed intermediates, 26199 Ethyl manganesepentacarbonyl, 32170 by rhodium catalysts, 289 instability, 32192 hydrogenation, 28107 synthesis, 32172-174 insertion into Mo-H bond, 12456 Ethyl-metal derivatives, 316-21 nickel-catalyzed oligomerization, selectiv- (1-Ethyl-1-methylpropyl)trichlorogermane, ity control, 12121-123 3218 oligomerization, 16257 Ethyl rheniumpentacarbonyl, 32170 catalyzed by organolithium reagents, reactions 1862-65 alkyl migration, 32210 oxidation to acetaldehyde with palladium with transition metal hydrides, 32206 chloride, 5321-352 synthesis, 32176 in aqueous media, 5323 Ethylsodium, crystal structure, 27:193 mechanism, 5330-339 Ethynylcopper compounds, reactions with deuteration studies, 5320 aryl halides, 12:277-278 kinetics, 5329 Ethynyl ligands, 38100-101, 139 in non-aqueous media, 5324,343-346 Ethynylsilanes, charge transfer complexes mechanism, 5346-349 of, 34155 reaction in presence of copper(I1) salts, 5339-343 Ethynyltrimethylsilane, 32247 palladium-catalyzed cooligomerization [Et4N]2[Bi3(Fe(CO)3)3BiFe(C0)4,structure with butadiene, 12179 and bonding factors, 4255 platinum chloride complex, 348 Europium polymerization, catalyzed by bisbenzene dicyclopentadienide, 9:380 chromium complexes, 13:69 graphite intercalation compounds, 2897 reactions with transition metal hydrides. mixed alkali metal compounds, 22215, 2244 256 rhenium carbonyl complex, 349 Europium complexes rhodium cyclopentadienyl complex, 349 divalent cyclopentadienyl, 24158 self-metathesis, 12457-458 pentamethylcyclopentadienyls, 24:165 structural change on coordination, 2k73 Exchange of groups Ethylene glycol, from synthesis gas, NMR study, 3156-159 1280-83 on organolead and organotin compounds, catalyzed by rhodium cluster, 1280-81 2271 Ethylene hydroformylation reactions, com- Exchange reactions puter representation, 26199-202 diborane and alkyl- or arylborons, dissociative catalytic cycle, 26:202-203 3266-267 via intramolecular carbonylation, diboranes, 3274 26:202-203 hydrogen-deuterium, 15148-149 with rhodium catalyst, 26199-202 in phosphine ligands, 15154-156 synthetic sequences, 2k200-201 in main group metal-transition metal with tungsten catalyst, 26199, 202 bonded compounds, 16117-118 Ethylene ruthenium(0) complex, 29:180 metal carbonyl derivatives, 3192-193 Ethylene ruthenium(I1) derivatives, 29175 nickel complexes, 3250 Exchange reactions 116

in organo-Group I11 compounds, Fe3(CO),]Bi2,synthesis, 4293 16116-129 [Fe2(CO)cJ3i2(p-CO(C0)4]]-,structure and organolithium compounds, 3381-383 bonding factors, 4250 radiochemical. 11:219 Fe2(CO)x(BiR)2,structure and bonding fac- Exchangc reactions, organometallic com- tors, 426 pounds, 8167-205,109 Fe4(CO)l,l(COEt)(PR)2,synthesis, 42119 bcryllium alkyls, 8170-171 Fe2(CO),]E[Fe2(CO),Cl], synthesis, 42107 cadmium alkyls, 8174-175 Fe3(CO)9[EML,)r,synthesis, 4279 Grignard reagents, 8171-173 Fe2(CO)6E4&, structure and bonding fac- isotopic exchange in ferrocencs, 1080 tors, 4264 of ligands, 1091 [Fc2(C0)&-GeMe2),, synthesis. mercury alkyls, 8176 42:253-254 organoaluminum compounds, 8179-183 [F~(CO)(T~-C~H~)]~,optical limiting proper- organo-Group 111 compounds, W87-203 ties, 43399 organolithium compounds, 8168-170 [Fe(CO)3]2(p-CO)(p-SiMe,),,synthesis, 111 8196-198 tetraalkyl-Group anions, 42244, 248 zinc alkyls, 8173-174 {Fe(CO)3)2(p-CO)(p-SiPhH)2,synthesis, Extended Huckel calculations, iron alkynyl 42235-236 complexes, 3883 (Fe(CO)3)2(~-CO)(p-SiPhMe),,synthesis, Extended Huckel molecular orbital calcula- 42234 tion, 39:53 [Fez(CO),{ p- 7’: Extcnded X-ray absorption fine structure, $-E= main group-transition metal clusters, C(Me)H)(Mn(Co)2(~~-CsH~M~)l*l, 42128-129 synthesis, 43172 Extrusion, of dinitrogen from platinum com- [Fe,( CO),{p-7’ :q2-Se-CH2)2], synthesis, plex, 12:74 43172 Extrusion reactions, computer representa- [Fez(CO)$ p-S=CH2Te]],synthesis, 43172 tion, 26177-178, 189-190 Fe3(C0)9(NMe)2,synthesis, 42121 feasibility matrix, 26:189 Fe4(CO)Il(NO)N,synthesis, 42116 Fe3(CO)loNSiMez,synthesis, 4283 [Fe,(CO),P,]-, synthesis, 42118 F Fel(CO)IoPCH(SiMe3)2,synthesis, 42108 Fe2(CO)7(PCr(C0)5]2, synthesis, 42108 Facile decarbonylation, manganese alkylpen- 422% tacarbonyls. 32173 Fe3(C0)9(PFp](PH),synthesis, [Fe(CO),PZ], synthesis, 42:110 Fast atom bombardment mass spectrome- try, of heteronuclear clusters. F~~(CO)~(P(OM~)~I~(PM~(CO)ZC~I{PI, 29304-305 structure and bonding factors, 4221 [Fc-(E)-CH=CHC6H4.4-N02],nonlinear op- Fe5(CO)I,( P) [ PMn( CO)2CP), structure and tics, 42328 bonding factors, 4239 Feasibility, of transition metal reactions, ac- [Fez(CO)&( P2Rz)2,synthesis, 42120 cording to computer surveys [Fe3(C0)9PR]2-,synthesis, 42117 extrusion rcactions, 26190 Fe3(C0)9(PR)2, synthesis, 4292 migratory insertion, 26188 Fe3(CO) 12PR,synthesis, 4297 oxidativc addition reactions, 26182 Fe>(CO),(PR)(PMe), synthesis, 42112 oxidative coupling, affording four-mem- [Fe(C0)4]3P4,synthesis, 42103 bercd metallacycles, 26:187 [Fe5(C0)12S4]2-,synthesis and structure, reductive elimination, 26:183-184 4k260-261 Fe3(CO)sAsZ.synthesis, 4286 [Fe6(C0)12S6]2-,synthesis and structure, [FQ(CO)~ASS]-,structure and bonding fac- 4k261-262 tors. 4246 [Fe3(CO)9[SbFe(CO)4)2]2-,synthesis, 42:111 117 Ferrocene

[FeZ(CO),(p-SC(Ph)=C(H)Se]],synthesis from alkali metal cyclopentadienide and and structure, 4k277, 284 metal salt, 2:379 [Fe,(CO),[p-SC(Ph)=C(H)Te]], synthesis aromatic substitution, 2k2 and structure, 41:277, 283 with azo-substituent, 21:32 [Fe2(CO),[p-Se~)z(p-S-truns-C4Hz)],synthe- bis(alkeny1) derivatives, 2k40, 43 sis and structure, 41:279, 285 bis(dimethy1amino) derivatives, 2k30 [Fez(CO)6(p-SeC( Ph)=C(H)Te]], synthesis bridged, 3:114, 135-149 and structure, 4k277, 282 charge transfer complexes, 33107-109, [[Fez(CO)~(Sez)l~(p-HC-C(C=CMe))l, 111-117 synthesis and structure, 4k281, 286 I3C NMR relaxation times, 19261-262 [Fez(CO),( Sez)[p-HC= C(C= CMe)]], syn- from cyclopentadiene, 2369 thesis and structure, 41:281, 285 and basic metal salt, 2372-373 Fe3(CO)&)(PR), synthesis, 42113 cyclopentadienyl ring orientation, [Fez(CO),STe,(p-HC=C(C=CMe))] mo- 40:118-119 lecular orbital calculations, 41:283, 289 diacetyl, 2k2, 8 [Fez(C0)$Te2 [p-HC= C(C =CMe) )] mo- dicarbomethoxy derivative, 21:7-8 lecular orbital calculations, synthesis dichloroboryl, 10263 and structure, 41:283, 288 discovery, 1320-21 [Fe5(C0)14Te4]2-,synthesis and structure, disilyl, 21:37 4k254-255 electrolytic reduction, 2k4-5 [Fe,(C0)20Telo]2-,synthesis and structure, electronic effects, 1079-111 41:254-255 electrophilic substitution, 1081 [(Fez(Co),)(~4-Te)(~L3-Te)IRU.7(Co)lI)l> formation synthesis and structure, 4k273-274 from other a-cyclopentadienyl com- Fez(CO)&, Fenske-Hall calculations, 4245 plexes, 10383-384 Fe3(C0)9(X)(PR),synthesis, 4299 of a-arene-a-cyclopentadienylironsalts, [F~~M~(CO)~~(~CL~-S~)Z(~~-T~)ZI,synthesis 10407 and structure, 41:301, 303 frequency assignment, k266-267 [FeZMozS2(CO)Iz]2-.synthesis and structure, homoannular, 1080 4k262, 264 from iron pentacarbonyl, 2373-374 [Fe6MoS6(C0)16]2-,synthesis and structure, isotopic exchange reactions, 1080 4k262 ligand exchange, 1044 [Fe4MoS3(CO)13(PEt3)]z-,synthesis and mass spectrum, 6285-286, 8241-242 structure, 4k262-263 molecular mechanics calculations, Fenske-Hall calculations, 26157 40:135-136 in dimetallacyclobutadienes, 26100-102 molecular orbital calculations, 40:132-133 Fenske-Hall method, iron-alkynyl com- molecular orbitals, 26:157-158 plexes, 3883 Mossbauer spectroscopy of substituent ef- Fenske-Hall model, 3476 fects, 40157-160 Fermi contact interaction term, 2140 neutron irradiation, 1k223 Ferrasilacyclopentane complex, 1k294 nucleus, 37:146 Ferricinium salts, 10407 oxidation, 2384 cyanation, 1039 to ferricinium, 26158 l-Ferrio-1,2-diphosphapropene,synthesis a-bonding, 1:3 with phosphaalkenes, 4k6 percyanovinyls, 2k44 l-Ferrio-2-phosphaarsirane, synthesis with phase-transfer-catalyzed substitution, phosphaalkenes, 41:s 19207 Ferrocene, 1:1,24,1320-22,26140 photoinduced electron transfer, absorption spectroscopy and substituent 33109-111 effects, 4&133-135 relative site reactivities, 1080 Ferrocene 118

ring cleavage, 19:117-120 [2]Ferrocenophanes, bimetallic complexes, stability of a-carbonium ions, 1043 37:283 structural distortions induced by bulky hydrocarbon-bridged, ring-opening poly- substituents, 40136-138 merization, 37:156-158 structure, 594 [3]Ferrocenophanes, 37: 16 1 substituted, 3127-129, 135-149 bimetallic complexes, 32290 mass spectra, 8242-257 Ferrocenylallenylidene complex, 3251 substituted compounds. electrochemical Ferrocenylammoniuni salts behavior, &149-150 anion exchange reactions, 1043 substitution reactions, 1321 photolysis, 1042 synthesis, u-cyclopentadienyl intermedi- Stevens rearrangement, 1044 ates, 16:246-247 Ferrocenylarsines, 4220 theoretical studies, 156, 32-33 Ferrocenylboric acids, synthetic utility, calculation of ionization energies, 159 1041 Ferrocene-based polymers, 37:134-136 a-Ferrocenylcarbonium ions, stabilization, Fcrrocene derivatives 10107 chemistry developed by Russian School Ferrocenyl complexes (Nesmeyanov), 1037-44 bimetallic, 3E280-288 chronopotentiometry, 1098, 100 carbene, 32289, 291 dissociation constants, 10106 carbyne, 37:291 heteroannularly substituted, NMR spec- third-order nonlinear optics, 43368-370, tra, 10:102-104 392. 395-398 interannular electronic effects, 1040, 101 Ferrocenyl derivatives, anion radicals, IR spectra, 10104-106 15312 Ferrocenyllithium, 37:140, 280 mass spectra, 6304, 308-310 Ferrocenylphosphines, as ligands for asym- mass spectrometry, 1095-97 metric hydrogenation catalysts, oxidation-reduction potentials, 1098 12348-349 with polysilane groups, 6:70 Ferrocenylsilanes. 433 cleavage of Si-Si bond, 674-77 [Fe2Ru&4-Te)z(CO), synthesis and struc- properties, 696-98, 102-103, 105, 108 ture, 4k271 primary substitution reactions, 1039 [FeS(pL?-S)2(CO)#, synthesis and struc- Ferrocene-organosilane polymers, by con- ture, 41:265-266 densation routes, 37:136-137 [{ Fe~Sez(CO)&p-PC-t-Bu)Fe2Se( CO)6], Fcrrocenophanes, 8254-255 synthesis and structure, 4k274-275 6305 fragmentation patterns, IFei(Se,),(cO),"][SbF~]*S02,synthesis and II jFerrocenophanes, 37162 structure, 41:246-248 bimetallic complexes, 32282 [Fe,( Se&( CO) I 21 [SbF&3S02, synthesis and germanium-bridged, ring-opening poly- structure, 4k247-248 merization, 37:152-153 [FeW( Se),( co)~][SbF&,synthesis and phosphorus-bridged structure, 4k245-246 properties, 3R154-155 Films, see Chemical vapor deposition ring-opcning polymerization, Fischer carbene complexes, see (1-Alky- 32153-160 ny1)carbenes synthesis. 32154-155 Fixcher carbenes, annulation of alkynes, silicon-bridged, 37:163 U278-287 properties, 37937-139 Fischer-Hafner synthesis, of arenemetal ring-opening polymerization, complexes, 1348-49, 63. 91, 93, 111 37136-151 Fischer-Tropsch catalysis synthesis, 37:137-139 by alkali metal GIC, 28111-113 119 Fluorocarbons

alternative mechanism for, 28176 Flash vacuum thermolysis, iminosilanes by, Fischer-Tropsch process, 20:3, 3574 39:161 and p-methylene complexes, 20228-231, Fluorenylidene germene, 39:284 248,250 Fluorenyllithium, bonding geometry, 22177 Fischer-Tropsch reaction, 1261-100,320, Fluorenyllithium complexes, 26:219-220, 373-375 222-223, 225 heterogeneous catalysis, 1262-64 Fluorenylpotassium, bonding geometry, iron, 1263 22177 historical aspects, 1262-64 Fluorenylpotassium TMEDA complex, homogeneous catalysis, 1265-66,73-79 26224-225 carbonyl clusters, 1275-79 Fluorides, organic, 3860 catalyst design, 17:73-75 Fluorine inactivity of mononuclear species, coordination in organoaluminum com- 1275-76 pounds, 9266-268 product distribution, 1278 ligand with a-fluorine, 3k200-201 selectivity, 1266 coupling, 31:201 industrial usage, 1762-65 fluoroacetylene complex, 31:201 lower olefins from synthesis gas, 1298-99 perfluorinated ligand, 3k183-267 mechanism, 1286-96 definition, 31:184-185 via carbene intermediates, 1290-93 Fluorine shift, in fluoroalkylboron com- via carbonyl insertion, 1287-88 pounds, k155-156 dual coordination of CO, 1288-91 Fluoroalkenyl, transition metal compounds preparation, k178-186 via hydroxycarbene condensation, 1286-87 properties, 1:186-195 Fluoroalkyl, transition metals, M69 via metal carbides, 1286-87 Fluoroalkyl-metal compounds, 326-29 methanol to gasoline, 1296-98 Fluoroarene complexes, 32293 zeolite-based catalysts, 17:96-98 Ffuorocarbanion, 1:146 new technology, 1296-99 Fluorocarbon complexes organometallic chemistry, 1266-86 mass spectra, 6:292, 302 metal formyl complexes, 1267-68 structures, 5125-128 1268-73 reduction of coordinated CO, Fluorocarbon-metal complexes, 8221-222, and shift reaction, 1283-86 262-263,270-272,274-275,279,281 synthesis of ethylene glycol, 1280-83 Fluorocarbon-metal derivatives, k143-220 catalyst loss problems, 1281 fluoroalkenyl compounds, 345-46 commercial viability, 1282-83 fluoroalkyl compounds, 326-29 use of heterometallic clusters, 17:82 perlluoroacyl compounds, 3:31 rhodium cluster catalysts, 1281-83 perfluoroalkyl compounds, 3:26-29, 31, Fischer-type alkylidyne-metal complexes, 35 35139 perfluorophenyl compounds, 343 Flash photolysis of metal carbonyls perfluorovinyl compounds, 343-45 in gas phase, 25283-284 Fluorocarbons in solution, 25S3-283 addition to nickel isocyanide complexes, unimolecular processes, 29284-286 1k73-74 electronic excited states of organome- hydrocarbon comparison, 3k183-184 tallic species, 25285-286 octafluorocycloocta-l,3,5,7-tetraene isomerization, 25284-285 cyclooctatetraene comparison, 3k202 Flash vacuum pyrolysis isomerism, 31:202-203 silenes by, 3985 reduction, 3k204 triazide(phenyl)silane, 39189 synthesis, 31:202 Fluorocarbons 12c

unsuccessful complex preparation, Formic acid, catalytic decomposition, 3k204 12383,22:140-142 perfluorinated ligand, 3k183-267 Formyl complexes, 201-37 perfluorobenzocyclobutene, 3k222 alkylation, 2018-21 perfluorobicyclo[4.2.O]octa-2,4,7-triene, anions, 205-9 cobalt, and rhodium complex, via formic acetic anhydride, 205 3k217-221 ion pair formation, 2013 perfluoroolefin complex, 3k191-194 bis(formy1) complexes, 20:9, 23-25 perfluorotricyclo[4.2.O.O]octa-3,7-diene with bridging formyl, 2033 iron complex, 3k214 as catalytic intermediates, 202-3,34 manganese complex, 3k210-211 cations, 20.12-13 transition metal compound, 3k183-267 decomposition, 2026-29 unsaturated kinetics, 2026 metallation reaction, 31:200 hydride transfer to metal carbonyls, perfluorocyclohexa-1,3-dienecobalt 2017-18 complex, 3k200 via hydrolysis of thioformyls, 1267 Fluorogermanes, 9:264 intermediacy in Fischer-Tropsch reac- Fluoromethylidyne complex tion, 1268,374-375 bridging, 3k190 of iron, 17:67 difluoroacetylene, 3k191 decarbonylation, 1267 Fluoroolefin complexes, 1525-26 IR spectra, 2013-14 '9NMR studies, 1526 kinetic stability, 2031-32 photoelectron spectroscopy, 1526 from metal carbonyls and trialkoxyboro- UV spectroscopy, 1526 hydrides, 1267 Fluorophosphinogermane, 39289 neutral species, 205,9-12 Fluorosilanes, 9262 NMR spectra, 20:13 complexes with organoaluminum com- photochemical loss of CO, 2025 pounds, 9268 protonation, 20:21-23 Fluorosilylamines, lithiated, 39164-165 reduction, 2023-25 (Fluorosilyl) lithium, 38:21, 47 of ketones and aldehydes, 2016-17 Fluorostannanes, 9264 synthesis, 203-13 (Fluorostannyl)silylphosphine, thermolysis, via $-formaldehyde rearrangement, 39310 2011 Fluorovinylgermane, 39289 hydride addition to carbonyl ligand, Fluxional behavior 204,8, 11 or organotransition metal n-complexes, from paraformaldehyde, 2012-13 1621 1-239 via thioformyls, 209,11 or polyene metal tricarbonyls, 16234-236 thermochemistry, 2029-31 Fluxionality thermodynamic stability, 204 cyclopentadienyl-bridged dipalladium X-ray structures, 2014-15 complexes, 19168 resonance description, 2014-15 1,4-diaza-1,3-butadiene complexes, Formyls 2k210-212 spectroscopic data, 28:151-155 Fluxional molecules, study by I3C NMR structural data, 2tk150-152 spectroscopy, 12:146-150 Fourier transform NMR spectroscopy, and Force constants, germenes, M120 stereochemical nonrigidity, 16319 Formaldehyde, reaction with phosphine, Fragmentation reactions, of metallacycles, 38165 computer representation Formate complexes, 22136-145 five-membered, 26185-186 decarboxylation, 22139-140. 144-145 feasibilitv matrix. 26186 121 Gallium

metallacyclopentane intermediates, HOMO orbitals, 36:68 26186 Hiickel energy levels, M60 four-membered, 26187- 188 interstitial substitution, 36.77-80 Free radical chain mechanism, organotin hy- ionization energies, 3659 dride additions, k63, 70, 75, 79-80 isomer behaviors, 3666 Free radical mechanisms, computer repre- LUMO orbitals, 3668 sentation, 26195-197 metal-containing substituents, M69-77 Free radicals Fourier transform mass spectra, 3676 in organometallic chemistry, 14345-392 iridium complexes, 3676-77 studies of H. Gilman, 228 naked metal complexes, 36:74, 76-77 Friedel-Crafts reaction osmate esters, 3669-71 acetylation of arene chromium tricarbo- platinum complexes, X71-72 nyls, 1385 ruthenium complexes, 36:74 acylation structures, N70, 72, 74-75 of a cobaltacarborane, 14178 Vaska’s compound, 3672-73 of H~C=CHCCO~(CO),,14125 NMR spectroscopy, 3659-60 in synthesis of alkylidynetricobalt nona- preparation, 3661-62 carbonyls, 14106-107 salt formation, 36:80 Frontier orbitals, and nucleophilic displace- separation, 36:62 ment at silicon, 20287-309 X-ray diffraction data, 3658-59 Fullerene complexes, third-order nonlinear complexes, 10178 optics, 43:385, 388, 391 , see also Pseudohalides Fullerenes, 3236 properties, 5218 alkali metal intercalation, 36:77-80 Fulvalene complexes, of dicarbonyl cobalt, electrical conductivity, 3679-80 2k28 structural studies, 3678-79 Fulvalene ligand, 32280, 303 synthesis, 3678 Fulvalenetitanium complexes bond distances, 3659 of dinitrogen, 1926-28 doped species, symbolism, 3658 hydride, 195-7, 10,22,31 electron affinity, 3659 Fulvene complexes, 34316-319 endohedral complexes, 3663-68 iron carbonyl, k36-37, 42 ESR spectroscopy, 3tk65, 67 Fulvenes EXAFS data, 3665 reactions with metal atoms, l378 formation mechanisms, 3664 from thiobenzophenones, 19189 fragmentation patterns, 3664 Fumaric acid, catalyzed hydrogenation to molecular orbital calculations, 36:67-68 succinic acid, 16263-264 Mossbauer spectroscopy, 3665 Furanoid carbene complexes, 32290 sequestration, 36:65-67 Furanoid glycals, synthesis, 28:117-118 synthesis, 3663-64 framework carbon substitution, 3680-86 calculated structures, 3684-85 G Car-Parrinello method, M83 Gadolinium complexes, in NMR studies, CBN-ball structure, 3684 16219 computational studies, 36533-86 Gallium heterocluster synthesis, 3682-83 alkoxides, 3939-44 hybrid clusters, 3680-81 amides, 3918-26 polymer formation, 36%1 anionic hydride complexes, spectroscopic general properties, 3658-61 properties, 27:6 Hartree-Fock method, 36:68 arsenides, 3926-28 heteroatom incorporation, 3658 aryloxides, 3939-44 Gallium 122

bisthiolates, 3946 cationic cluster, 3k107 bridged electron-deficient compounds, structure and bonding, 3k108 15244,250-251 Gallium, n complexes halides, reaction with carbene complexes, alkyne complexes, 26244-246 14:27 arene complexes, 26:245, 247-248, 287 heterocarborane, 30112-116 cyclopentadienyl complexes, 26:245-246 bonding, 30115-116 dicarbollyl complexes, 26245-247 preparation, 30112-113 mesityl complexes, 26245, 247-248 structure, 30:114-1 IS structures, 26245 monothiolates. 3946 toluene complexes, 26:248 multiple bonding, 392 Gallosiloxanes, 9274 organometallic compounds, 392-3, 6 Galvinoxyl, as radical inhibitor, 14347, 380 phosphides, 39:26-38 Gamma ray resonance spectroscopy, see siloxide, 3941 Mossbauer spectrometry terphenyl derivatives, 4425-27, 29 Gas, ambient, effect on sonochemistry, tetraorganodimetallanes, 396-13 2590 Gallium complexes Gas-phase electron diffraction benzene, 26217,245,247-248 bis(pentamethylcyclopentadieny1)magne- borane, 2k63-64 sium, 32158 rhenium, 3956 cyclopentadienylneopentylrnagnesium, transition metal, 3948-49 32158 Gallium, indium, and thallium transition dicyclopentadienylmagnesium, 32158 metal complex dineopentylmagnesium, 32158 alkyl and aryl metal amide, 3k271-273 disadvantages, 32157-158 cobalt, 3k106-107 metallocenes, 40:145, 246 anionic, 3k106 organomagnesium structural chemistry, heterolytic bond dissociation, 3k106 contribution to, 32159 preparation, 3k106 Gaussian enhancement, of NMR spectros- structure, 31:106 COPY,B399-400 cyclic and chelated amide, 3k273-276 Gematetrazolines iron and ruthenium anionic cluster, cycloreversion reactions, 24:232-233 31~101-106 synthesis, 24204-205 bonding, 3k103 thermolysis, 24:232-233 bridging thallium, 3k105 Geminal polyhalides, reduction by organo- formation of larger cluster, 3k102-103 tin hydrides, k71 preparation, 3k101, 105 GEOME calculations, 36124 manganese and rhenium LGermaallenes cluster formation, 3k98 physical properties, 44.165-166 isolobal bonding, 3k102 reactivity, 44166 mixed metal species, 3k99-101 synthesis, 44164-165 polar bonding, 3k97 2-Germaazetidine, 3%299 preparation, 3k96-100 Germabcnzenes, 2k249 reaction pentacarbonyl species, 3k97 Germachalcogenones, theoretical studies, molybdenum and tungsten 44154 aluminum comparison, 3kYS-96 Germacyclobutanes, 2k243 bond length, 3k93-94 mass spectra, 2k282 ionic metal-metal bonding, 3k95 Germacyclopentenes, 13151, 153, 157-158 preparation. 3k92, 95 Germadienes, geometry and bonding, structure, 3k92-93 44:121-122 platinum [l]Germaferrocenophanes, 32152 123 Germanium compounds

Germaimines contrasts with silicon, 916 1,2-cycloaddition reactions, 21:266-268 dichloride dioxane, in digermene synthe- with carbon disulfide, 2k267 sis, a129 with germylenes, 21:268 dicyclopentadienyl, Pk128-129 with isocyanates, 2k266 germanium-germanium bond formation with isothiocyanates, 2k266-267 dehydrogenative coupling, 43245-246 1,3-cycloaddition reactions, 2k268-269 demethanative coupling, 43246-248 with ethylene oxide, 21969 heterocarboranes, 3L127-130 from cyclogermazanes, 21:265 bipyridine adduct, 30128-129 catalytic depolymerization, 2k265 geometry, 30127-130 infrared study, 2k281 structure, 30227-131 MO calculations, 2k279 synthesis, 30:117, 127-128 structure, 2k279-280 ionic structure, 39283 reaction with pinacol, 2k263 mixed alkali metal complexes, 22218, synthesis, 21:262-266 224,232-233,252 trapping reactions, 2k265-266 organic derivatives, 43847 1-Germaindenes, synthesis, 42158 organometallic compounds, synthesis, Germanes, synthesis, 39302-303 39:2 Gerrnaneselones, 39285, 290 terphenyl derivatives, M.33-39 physical properties, 44:159-162 tetraethyl, irradiation, 1k218, 222 reactions, 39298, 301 in triosmium clusters, 26:69-70 reactivity, 44162-163 Germanium-bridged [l]ferrocenophanes, synthesis, 44:155-159 ring-opening polymerization, Germanetelones, 39290 32151-153 physical properties, 44:159-162 Germanium compounds synthesis, 4.4155-159 cage and cluster, 321-14 Germanethiones, 39283,285 hexagermaprismane, 37:l-2,26-29, 31, complexes, 39290-291 36 physical properties, 44.159-162 octagermacubane, 322, 17-19 preparation, 39:290 double bonded, 39275-304,320 reactions, 39:291, 293, 298, 301 properties, 39:276-287 reactivity, 44:162-163 reactions, 39290-304 synthesis, 44.155 -1 59 spectroscopy, 39283-286 Germanimines synthesis, 39:287-290, 320 complexes, 39:290-291 nitrogen, 3398-412, see also Organoger- molecular structure, 39282 manium-nitrogen compounds physical properties, el48 redistribution equilibria, 6:236-242 preparation, 39:288-290, 294 Germanium compounds, structure and reactions, 39:291, 293, 297-298, 300-301 bonding reactivity, 44:148-150 bond dissociation energies, 33129-132 spectroscopy, 39285 M-H and M-M, 33:130 synthesis, 44:144-148 bond energies, 33135 Germanium bonding considerations anionic hydride complexes, spectroscopic CH, compounds, comparisons to, properties, 224-5 33135 applications of organogermanes. 43198 Jahn-Teller effect, second-order, bis(bistrimethylsilyImethyl), 19136-137 33135,138 carbon bond formation, see Carbon-ger- MR2 compounds, 33137-140 manium bond formation MR3 compounds. 33135-136 chalcogen bond, heterocycles, 4k155-156 parent hydrides, 33:135-140 Germanium compounds 124

divalent state stabilization energies, chromium, molybdenum, and tungsten 33131-135 bond length, 3k111 RR’M, preferred values for, 33:131 cyclopentadienyl ligand, 31:108-109 doubly bonded isocarbonyl bridging, 31:llO bond energies, 33141, 143-145 mixed metal species, 3k113 digermene, 33152, 154-158 substituted cyclopentadienyl ligand, divalent state stabilization energies, 3k109-110 33141,143-145 three transition metal, 3k110 germasilene, 33:153, 156-158 cobalt germene, 33146-147, 149-150 high nuclearity cluster, 31:125-126 isomeric energy differences, 33141, 143 oxidation divalent species, 31:123 triply bonded spirobicyclic, 3k124 digermyne, Ge2H2. 33161-163 synthesis divalent germanium species, electronic structure vs. stability, 31:122-123 33:163-164 tetracobalt cluster, 31:123 structural complexity, 33161-162 tin and lead preparation, 3k124 substituent effects, 33164-165 iron Germanium compounds, with multiple carbonyl bridging, 3k120 bonds, 2k241-286 carbonyl cluster, 3k117, 120-122 to bismuth, 2k274 mixed metal, 3k119 to carbon, 2k243-250 spirocyclic tetra-iron species, between germanium atoms, 21:272-274 3k118-120 IR spectra, 2k281 tetrahedral tetra-iron, 31:121 to manganese, 21:274-276 tetra-iron species, 3k117 mass spectra, 2k282-283 tri-iron species, 3k117 MO calculations, 21:275-281 manganese to nitrogen, 21:255, 263-269 conformer, 3k115 to oxygen, 2k250-253, 255-262 linear two-coordinate geometry, to phosphorus, 2k269-272 3k115-117 photoelectron spectra, 21:281 multiple bonding, 31:113-116 to sulfur, 21:252-255, 257-262 triple bond character, 3k115 Gcrmaniurn hydrides mixed transition metal kinetic isotope effects, 44AO3-104 cobalt-iron cluster, 3k129-129 reactions cobalt-molybdenum, 31:129 with carbon-centered radical, 44.86. 88 cobalt-nickel, 3k129 with oxygen-centered radical, 44538, 90 iron-rhenium cluster, 3k128-129 Gcrmanium organoselenium derivatives, nickel cluster 582 carbonyl, 31:127 organosulfur derivatives, 552-54, 59, 65, icosahedral, 3k128 67,69,71-74, 76-78, 80-81 pentagonal antiprismatic, 3k127 organotellurium derivatives, 582 spectroscopic study, 31:129-130 Germanium, ?r complexes, 26:258-267 Germanocene, see Dicyclopentadienylger- carbollyl complexes, 26266-267 manium of cyclopentadiene, 26258-266 Germanocenophanes, 26258 mixed-metal complexes with arsenic, Germanols, 9:269 X267 alkali metal derivatives, %272 mixed transition metal complexes, 26266 Germanones, 2k247.250-253,255-256,268 structures, 26260 addition reactions, 21:257 Germanium, tin, and lead transition mctal cycloaddition reactions, 21:257 complex with 1,3-dipolar reagents, 2k260-262 125 Gerrnylene Complexes

by germylene oxidation, 21:255 MO calculations, 21:278-279 insertion and ring-expansion reactions, palladium complexes, 2k257 2k257 reduction by trialkylphosphines, 2k257 with oxiranes, 2k258-259 Germazanes, 3400,406 in mass spectra of digermoxane, 2k283 Germenes, 2k244-250 MO calculations, 2k278-279 addition reactions, 2k244-245 polymerization, 2k250 to methanol, 2k245 reactivity, 44.151-154 to phenol, 2k244 reduction by trialkylphosphines, 2k257 complexes, 39290 synthesis, 44d51-154 cycloaddition reactions, 2k247 theoretical studies, a154 with diphenylnitrone, 2k247 trapping reactions, 2k251 with nitrosobenzene, 21:247 Germaoxaazetidines, 2k255-256 fulvene derivative, 2k250 Germaoxacyclohexene, 39296 from germylenes and diazo compounds, Germaoxadiazolines, 2k260-261 2k246 Germaoxaphosphetanes, 39298 halo derivatives, 2k247-249 2-Germaoxetanes, 39296 MO calculations, 2k275-277 3-Germa-1-phosphaallene molecular structures, 39281 physical properties, M167 by photolysis, 2k244 reactivity, 44d67-168 physical properties, 44:119-122 synthesis, a166 polycondensation, 2k247 Germaphosphenes preparation, 39:288-289 molecular structure, 39281-284 reactions, 39:2Yl, 294-295, 299-300, 302 physical properties, a151 reaction with benzaldehyde, 2k247 preparation, 39288-289 reactivity, U122-127 reactions, 39:291, 293, 298, 300, 302 spectroscopy, 39285 reactivity, a151 synthesis, M114-119 spectroscopy, 39:285, 308 theoretical studies, 44:119-122 synthesis, a150 Germirane, 39294 Germaphosphimine, 2k269-271 Germirine derivatives, dimeric nature, addition reactions, 2k26Y-270 13147-148 via exchange reactions, 2k271 Germole. rearrangements, 44A18-119 MO calculations, 2k280 Germoxanes, 2k250 4-Germa-l-pyrazoline, 39294 Germylazetidines, 2k263-264 Germasilenes, 39287, 289 Germyl cation, formation, 44A34 reactions, 39:291, 297, 301 Germyldiazenes reactivity, 44:139-141 electronic structure, 23139- 142 synthesis, a139 properties, 23138-142 Germathiadiazolines, 2k260-261 synthesis, 23:133-137 l-Germa-3-thietane, [2 + 21 cycloreversion, thermolysis, 23:145-149 44.117 Germylene complexes, bridged Germathiones, 2k252-254 carbonyl ligand removal, 42261 addition reactions, 2k257 fluxional behavior, 42275 cycloaddition reactions, 2k257 geometric isomerizations, 42279-284 with 1,3-dipolar reagents, 2k260-262 structure and bonding, 42265-266,268- from germylenes, 2k255 269,272 insertion and ring-expansion reactions, substituent replacement, 42262-263 2k253, 257 synthesis with cyclopropanes, 2k257 germylenesilylene unit, rearrangement, with oxiranes, 2k258-260 in a complex, 42260 Germylene complexes 126

halogermane reactions with carbonyl, methyl derivatives, 23:149 complexes, 42:2.57 tcrtiarybutyl derivative, 23:151 hydrogermane Germylphosphine imines, 9:308-309 elimination from bis(germy1) com- Germyltetrazenes plexes, 42258-259 isornerization, 24216-219 reactions with carbonyl complexes, photodecomposition, 24216 42253-256 physical properties, 24207-211, 215 miscellancous reactions, 42263-264 protolysis, 24:235, 237 overview, 42224,252-253 substitution reactions, 24237-239 salt elimination reactions, 42257-258 synthesis, 24202-204, 206, 208, 210 stable germylene reactions with com- thermolysis, 24220-228, 230 plcxes, 42259 Germyltriazenes p-Gcrmylene complexes, 20231 -237 physical properties, 24192-193 Germylenes, 39287 synthesis, 24180, 182, 187 -azide reaction, a146 Germyl triflate, 3210 and azides, 21:262, 267 Germyne, in digermene synthesis, a131 and benzaldehyde, 2k267 GIC. see Graphite intercalation compounds -chalcogene reactions, M156-158 Glycine, reaction with organoplatinum(1V) coupling reactions, 39289-290,294, 303, compounds, 27:119-120 U128-129 Glycolic acid, in spirocyclic A%-silicates, li- with carbenc, M116 gands, M241 with CS2,44:115-116 Glycosyl halides, 28117-1 18 -diazomalonate reaction, 44:144-145 Gold from digermene decomposition, a138 alkyls, redistribution reactions, 23120 from germanones, 21:257 cyanide derivatives, 5186 from germathiones, 2k257 mixed alkali metal compounds. 22250 in germene synthesis, 2k246 in triosmium clusters, 26:73-75 MO calculations, 21:276-277, 280 Gold adducts, to dXalkylidene complexes and nitrenes, 21:263 of Ru, Os, and Ir, 25166 and nitronc. 2k255 Gold clusters. 3591, 108 and nitrosobenzenc, 2k255 platinum, synthesis, 29258 and oxaziranes, 2k25.5 Gold complexes oxidation, 21:255, M152-153 alkyl, 38108 rearrangements, 44:118-119 alkylidene carbaborane sulfuration, 2k255 iron, 3k72-73 Germylformylation, 43241 molybdenum, 3k59 Germylgcrmylcne, 39303 alkynyl, 3889, 108, 111-113, 11Y Germylidene phosphanes, 39209 anionic hydride Germyl lithium structural characteristics, 2216 mangancsepentacarbonyl alkyl reaction, bimetallic, 32253, 255, 260, 277, 295, 305 32188-189 halide rheniumpentacarbonyl alkyl reaction, solubility, 29252 32209 synthesis, 29252 Germylmercury compounds, photolysis, isocyanide, lk41, 80-81 21:273 addition of azide, 1k41 Germ ylorganyldiazenes manganese, 3k14-15 properties, 23138-1 42 by metal atom synthesis, 15104 protolysis, 23155 p-methylenes, 20248 synthesis, 23136-137 organolithium derivatives, 24396-397 thermolysis, 23149-1 52 phenylethynyl, X131 127 Grignard reagents

phosphine, reactions with metal clusters, iron-graphite, 28:123-124 22:187, 189-190 magnesium-graphite, 28125-126 phosphine clusters, electron-transfer reac- nickel-graphite, 28121-122 tions, 24121-122 palladium-graphite, 28120-121 photochemistry tin-graphite, 28119-120 binuclear phosphinoalkyls, 24326 titanium-graphite, 28126-128 phosphine methyls, 24325-326 zinc-graphite, 28:113-115 tantalum, 3k29-30 zinc/silver-graphite, 28:116-118 vanadium, 3k24-26 Greenwood’s rule, 964 ylides, 20153 Grignard reactions, 3866-67 Gold heteronuclear clusters, 29249-250 catalyzed by organocopper complexes, of higher nuclearity, 29258 12283-285 with isocyanate ligands, 29259 of organozinc compounds, 12:103-112 with ligands other than two-electron do- in preparation of organocopper com- nors attached to IB metals, 29335 plexes, 12:217-221 of lower nuclearity, 29:258-259 Grignard reagents, 1014, 3859 metal core arrangements, 29316-317, 319 addition to with more than three Au(PR,) units, mesityl ketones, 1:228-230 29300-301 phenolic ketones, k235-236 Mossbauer spectroscopy of, 29304-307 polycyclic ketones, k223-228 with no ligands attached to Group IB systems of heterocyclic aromatic nuclei, metals, 29328 k232-235 synthesis unhindered ketones, k237 by treatment of cationic complex, Color Test I, 26 29259 constitution, 3158 by treatment of salt, 292.59 coupling by samarium chloride, 9:365 using anionic precursor, 29251 in direct arylation of Pd or Pt complexes, Gold-phosphorus bond, 38119 28221-226 Graphite discovery, 1311-12 intercalates of alkali metals, 2%206-208 group exchange, 8171-173 structural definitions, m86-88 with organo-Group I1 compounds, Graphite intercalation compounds 8176 alkali metal long-term stability, 7:7 as catalysts, 28:107-113 preparation from perfluorovinyl com- as reagents, 2899-107 pounds, k152 synthesis of, 2892-96 quantitative determinations, 75 classification of, 2888-92 reactions, 7:3-4 covalent, 2829 reaction with interaction with solvents, 28:97-98 allylic alcohols and nickel halides, interest in, 28.85-86 1%216 lamellar, 2889 diazoalkanes, 9428 metal, other, 289-97 digermenes, a138 nonmetal, 28128-130 germacyclopentenes, 13157 reactions, polystage vs. isostage, classifi- tin doubly bonded compounds, 39:313 cation of, 2891 redistribution reactions, 6205 residue, a89 structure, 4280-281, 283-285 stages, 28:86-87 sylene synthesis, 3974, 82-83 structure, 28539-90, 92 in synthesis of synthesis, 28536-94 alkylidynetriocobalt nonacarbonyls, Graphite surface compounds 14103-104 Grignard reagents 128

bisarenc complexes, 1261-62 Mn(C0)5CF3 ligand exchange, tertiary stibines, 14197 35221-222 Grimes’ isomers, 3636-37 Mn(C0)SCF3synthesis, 35221 Group 1 elements Mn(CO),COCF, decarbonylation, phosphinocarbenes R2P-C-X, a187 35222-223 terphenyl derivatives, 46-9 Group 8 metals, trifluoromethyl derivatives Group 2 elements cadmium complexes, 35224-227 hetcrocarborane, 30104-105 chromium complexes, 35225 terphenyl derivatives cis-Fe(C0)4(CF7)2,35224-225 Be compounds, 410-12 CpFe(C0)2CF3,,35223-224 Mg compounds, 44.13-14 Fe(diars)(CO)* I(C0CF3), 35225 Group 3 elements iridium complexes, 35224 heteronuclear multiple bonding, 3913-62 iron complexes, 35223-225 Main Group 3-4, 3993-14 mercury complexes, 35226 Main Group 3-5 and 3-6, 3914-47 molybdenum complexes, 35224 transition metal derivatives, 3947-62 osmium complexes, 35226-227 homonuclear multiple bonding, 397-1 3 Os(0) difiuorocarbene compounds, n-bonding, 393-4 35226-227 Group 3-4 elements, heteronuclear multiple Os(0) trifluoromethyl compounds, bonding, 3913-14 35226-227 Group 3-5 elements, heteronuclear multiple Ru(0) difluorocarbene compounds, bonding, 3914-47 35226-227 Group 3-5 metals, trifluoromethyl deriva- Ru(0) trifluoromethyl compounds, tives, 3921 8 35226-227 ruthenium complexes, 35226-227 cadmium complexes, 35218 ruthenium(I1) difluorocarbene com- hafnium complexes, 35218 pounds, 35226 zirconium complexes, 35218 ruthenium(I1) trifluoromethyl com- Group 3-6 elements, heteronuclear multiple pounds, 35226 bonding, 3914-47 tungsten complexes, 35224 4 metallocenes, third-order nonlin- Group Group 9 metals, trifluoromethyl derivatives, ear optics, 4x371-372 35:227-229 Group 48 metallocene dicarbonyls, see Car- cadmium complexes, 35227-229 bony1 complexes, Group 48 metal- cobalt complexes, 35227-228 locene Co(II1)- R, compounds Group 6 metals, trifluoromethyl derivatives, kinetics, 35228 35218-221 reduction, 35227-228 cadmium complexes, 35229-220 thermodynamics, 35228 chromium complexes, 35220-221 C~CO(CO)(CFJ),,synthesis, 35227 CpMo(CO),CF?, 35218-21 9 iridium complexes, 35229 CpMo(C0)3CF3 difluorocarbenes, Ir(II1) compounds, 35229 35219-220 mercury complexes, 35229 CPW(CO)I CF?, 35218-219 Rh( CO)(PPhj),( CF?), 35228-229 molybdenum complexes, 35218-221 rhodium complexes, 35228-229 tungsten complexes, 35218-220 Vaska’s complex, 35229 Group 7 metals, trifluoromethyl derivatives, Group 10 metals, trifluoromethyl deriva- 3522 1-223 tives, 35230-231 cadmium complexes, 35221 nickel complexes, 35230 manganese complexes, 35221-223 palladium complexes, 35230 Mn(CO)5CF3carbonylation, 35:222-223 platinum(I1) compounds, 35230-231 129 Group IV

platinum(1V) compounds, 35230-231 heterocarborane, 30:140-147 silver-assisted trifluoromethylations, ionization potential, 30198-199 35230 phosphinocarbenes R2P-C-X, M200- Group 11 metals, trifluoromethyl deriva- 203, 205-208 tives, 35231-232 terphenyl derivatives cadmium complexes, 35231-232 As compounds, 44.45-47 gold compounds, 35232 Bi compounds, M47-50 silver compounds, 35232 N compounds, 44:39-41 Group 12 elements, terphenyl derivatives, P compounds, 44:41-45 M18 Sb compounds, 4447 Group 12 metals, trifluoromethyl deriva- Group 16 elements tives, 35233-234 heterocarborane, 30147 cadmium complexes, 35233-234 phosphinocarbenes R,P-C-X, M208 Cd(CF3)2DME, 35233-234 terphenyl derivatives Hg(CF,)2, 35234 0 compounds, 44:50,52 mercury complexes, 35234 S compounds, 4452-55 zinc complexes, 35233 Se compounds, M55-56 Zn(CF& synthesis, 35233 Te compounds, M56 Group 13 elements Group 17 elements, terphenyl derivatives, heterocarborane, 3O:lOS-116 &56-58 Lewis acids, reaction with phosphinocar- Group I metal halides, reactions of 0s and benes, 44994, 196-197 Ru carbyne complexes with, 25191 terphenyl derivatives, 44.18-19 Group IVB halides A1 compounds, M23-25 and catalytic hydrogenation of poly- B compounds, M19-23 olefins, 16265-266 In compounds, M30 insertion into metal-metal bonds, 18:15, Ga compounds, M25-27,29 17-18 TI compounds, 44:30 Group IVB metal compounds Group 14 elements I3C chemical shifts of methyl derivatives, heterocarborane, 30116-140 12:167-168 hydrides insertion of dihalides into metal-carbon bond dissociation energy, M68-70 bonds, a75 kinetic isotope effects, M103-104 Group IV compounds, reaction with al- radical kinetic methods, 44,70-73 kenes and alkynes, 5240-242 reactions with radical Group IV elements germanium, hydrides, 44:85-90 metallocenes of, 26273 silicon, hydrides, &73-85 pentadienylmetal complexes, reactions of, Sn, hydrides, M90-102 26134-135 reactivities, 44:104-106 in triosmium clusters, 26:68-70 Lewis acids, reaction with phosphinocar- Group IV keto derivatives, %96-153 benes, U.193-194 Group IV organoselenium compounds, phosphinocarbenes R2P-C-X, M187- 581-83 194, 196-200 Group IV organosulfur compounds, 5:l-92 terphenyl derivatives action of heat, 521-22 C compounds, M31-32 alkali metal derivatives, 518-21 Ge compounds, 44.33-39 bond parachors, 543 Pb compounds, M33-39 cyclic derivatives, 53-6 Si compounds, M32-33 electron diffraction, 539 Sn compounds, 44:33-39 infrared and Raman spectroscopy, Group 15 elements 540-41 Group IV organosulfur compounds 130

group frequencies, 541 hexacarbonyls microwave spectra, 540 Lewis base derivatives, 1810 NMR spectra, 542 reaction with ammonia, 1819 oxidation, 323-24 reaction with bipyridyl ligands, 18:43 a-bonding, 547-48 thiocarbonyl derivative, 1818 properties, 551-83 a-complexes, 26:285-286 reactions with amines, 526 structures, 26:285 with bases. 524-26 pentacarbonyl dianion, 185 with covalent halides, 527-34 IR spectrum, 187 with hydrogen halides, 526 reaction with binuclear carbonyls, with sulfur, 522 18:15 with thiols, 526 reaction with Lewis bases, 1810-12 reduction, 524 reducing strength, 18:7, 10 syntheses, 53-23 tetracarbonyl trianions, 185 from alkali metal compounds, 5:19-21 trinuclear carbonyl anions, 186 by cleavage of metal-carbon bonds, Group VII metals 514-15 carbonyl complexes, photochemistry, metal-metal bonds, 515-16 26297-375 from halides, 53-10 71 complexes, 26:285-286 from hydrides, 516 structures, 26:285 from nitrogen and phosphorus com- Group exchange, organolithium com- pounds, 513-14 pounds, 8:168-170 from oxides, 510-12 Group frequency, k243, 246 X-ray studies, 538-39 Grubb’s reagent, M141 Group IV organotellurium compounds, 581-83 Group V compounds, reaction with alkenes H and alkynes, 5242 Group V elemcnts, pen-alkyls, 14205-243 Hafnium Group V1 metal carbonyls, amine deriva- his( 7-cyclopentadienyl) tives, 85 dicarbonylhafnium formation, 25336 Group VI mctal complexes, mass spectra, bis( 7-pentamethylcyclopentadienyl) 8:218-234 dicarbonylhafnium formation, a-arene, 8:227-23 1 25341 -342 a-cyclopentadienyl, 8218-227 “C NMR spectrum of butadiene com- Group VI metals plex, 19:276, 278 binuclear decacarbonyl dianions, 186 ( q-CSMe,)CpM(CO)* preparation, 25342 insertion reactions, 1815-18 Hafnium complexes, 35218 iodine oxidation, 1816 bimetallic, 32258, 263, 272, 278, 282 reaction with binuclear carbonyls, borane, 2k63 I815 dicyclopentadien yl structure, 187-9 dicarbonyl, 19:36 binuclear decacarbonylhydride anion, photolysis of dimethyl, 1915 186 electron-transfer reactions of cyclopenta- reaction with sulfur ligands, 18:13-14 dienyl alkyls, 23:44 structure, 188 phenylethynyl, 38122, 135-136 carbonyl complexes, photochemistry, 122-valence electron, 30:204 26297-375 128-valence electron. 30:201-204 chiral complexes, 18:162-163 Hafnocene complexes cyanocarbonyl anions, Nk12.36-37 s-cis-q4 -dienes, 247-9 131 Hammett up-parameters

automerization, 2411-13 with unsaturated germanium com- dynamic behavior, 249-13 pounds, 39:292-293 isomerization, 248-9 substituted carbon-centered radical, M97 NMR spectra, 213-15 Halogenation reaction with ethylene, 229 organocobalt compounds, 1k425 reactivity, 226-33 platinum( 11) complexes, 22114-1 15, u,rr-bonding, 224 120-121 structures, 2413, 21-14 Halogenoalkyl-transition metal complexes photochemistry of dialkyls, 24259 cphalogenoalkyl complexes, 33273-284 s-trans-q4-dienes, 24:3-7 monohalogenomethyl complexes bonding, 244 chromium, 33242-244 equilibration with cis-isomer, 24,8 cobalt, 33248-251 NMR spectra, 2413-15 gold, 33271-273 photoelectron spectrum, 2413 iridium, 33257-259 reaction with ethylene, 24:29 iron, 33236-240 reactivity, 226-33 manganese, 33246-247 synthesis, 244-7 molybdenum, 33245 Hafnocene monocarbonyl derivatives (‘I- osmium, 33241-242 palladium, 33259-261 CSMes)2Hf(H)2(CO)rformation, 25372 platinum, 33261-270 monocarbonyl-phosphine complexes, for- rhenium, 33247-248 mation, 25371-372 rhodium, 33251-257 Halide bridged complexes, 352-3 ruthenium, 33240 Halides tungsten, 33245-246 alkyl, Wurtz coupling of, 28100-101 Halogenocarbene complexes, heteroatom- glycosyl, 28:117-118 substituted carbene complex synthesis MC12,28221-222 from, 25142 arylation of, 28226-227 Halogenogermanes of mixed alkali metal compounds, adducts with nitrogen bases, 3398-400 22228-231 reactions with ammonia and amines, of triorganoplatinum(1V) compounds, 3~400-404 22126-127 Halogenometal carbonyls, 8:13 Haloalkanes, reactions with metal atoms, P-Halogenomethylene phosphoranes, a& 1562 elimination, M181-182 Haloarene complexes, 32292 Halogenonium salts, 106 Haloarsines, 4195-198 Halogermanes, dehydrohalogenation, Halobenzene, p-substituted, reduction with 39288 organotin hydride, k75 a-Haloketones, reduction with organotin hy- Halocarbonyl complexes, see Molybde- dride, 1:74 num(II), halocarbonyl complexes; Tung- Halomethyl complexes, synthesis of nonhet- sten(II), halocarbonyl complexes eroatom-substituted Os, Ir, and Ru car- Halocarbonyls, spectroscopic data, 28:153 bene (alkylidene) complexes from, Halogen 25160-161 addition to metal complexes, 7:77-79 Halopolysilanes metal interconversion reactions, 7:19-21 disproportionation, 6:28 reactions redistribution reactions, 629 with d8 alkylidene complexes of Ru, a-Halosilyl anions, 3&21 Os, and Ir, 25166 Hammett u-constant, for CCO~(CO)~,sub- of 0sand Ru carbyne complexes with, stituent, 14128 25192 Hammett up-parameters, correlations Hammett q,-parameters 132

with halfwave potentials of areneiron organogallium compounds, 272-73, 93 compounds, 13:98 organogemanium compounds, 2:75-76.93 with Jpt-Hin hydroplatinum complexes, organoiron compounds, 288-89, 95 13338 organolead compounds, 288-89,94 with Mossbauer data of areneiron com- organolithium compounds, 257-59, 91 pounds, 1398 organomagnesium compounds, 259, 91 with 'H NMR data of arenerion com- organomanganese compounds, 288,95 pounds, 1398 organomercury compounds, 262-66, 92 with vpt-ii in hydroplatinum complexes, organomolybdenum compounds, 290-91, 13:338 95 Hammett u-values, correlation with organonickel compounds, 289-90,95 chemical shifts, 12142 organophospshorous compounds, 281 - Hard and soft acid and base theory 82,94-95 and behavior of allylnickel catalysts, organoselenium compounds, 285-86, 95 12112 organosilicon compounds, 273-74, 93 and catalysts, 15148 organotin compounds, 276-80, 94 and r- vs. 8-bonding, 16243 organotungsten, 291, 95 Harmonic oscillator equation, k308 organovanadium compounds, 2:S6, 95 Hartree-Fock method, 3668 organozinc compounds, 259-61, 92 Hartree-Fock theory, molecular orbital coef- silenes, 2521 ficient assignment, 42:310-313 (HEB)Cr( CO)2L complexes, 34:299-303 HBF4 Et2O protonations Heck reaction, using Pd-gr, B120 bidentate phosphines, 35149-152 Heck-type arylation, 34134 monodentate Lewis bases, 39142-149 Hemoglobin, "C NMR spectrum of bonded HCFe,(CO)oAsM(C0)5, synthesis, 4289 "CO, l2:145 [(r/S-CsHS)2V(v2-S=CPh)],synthesis, 43146 Heptacarbonyl-p-q2 5.2-'-2,4-hexadiene-2,5- HID exchange, borabenzene metal com- diyldimanganese, 26355-356 plexes, 25230 Heptahydrotriborane, 2k77 Head-to-tail dimerization ally1 analogy, 21:77-78 iminosilanes, 39176-178 clusters, 2k96-98 silenes, 39105-106 metal complexes, 2k96-97 Heat of atomization Heptaphenyl-7- delinition, 251 borabicyclo[2.2.l]heptadiene,39385 table of atoms, 252 Heptaphenylborepin, 39:387 organometallic compounds, 2:91-95 Heptastanna[l.l.l.] propellanes, 38:236 Heat of redistribution, Allen bond energy, cis-Heptatriene, 39386 2107 Hetarylsilanes, charge transfer complexes Heats of formation of definition, 251-52 absorption spectra, 34.170-171 certain organic free radicals, 254 conjugation, degree of, 34:170 experimental measurement. 255-57 ferrocene, spectral characteristics with, hydrocarbon-metal complexes, 8286-287, 34172 320-32 1 Heteroaldehyde transition metal complexes ionic, 6316-323 bonding configurations and interactions, organoaluminum compounds, 271-72, 93 43128-131 organoantimony compounds, 284-85, 95 highest occupied molecular orbital analy- organoarsenic compounds, 285, 95 sis, 43127-128 organoboron compounds, 266-70,92-93 IR spectroscopy, 43135 organocadmium compounds, 261-62, 92 ligand dynamics organochromium compounds, 286-88, 95 7'-Elv1-Z isomerization, 43134 133 Heterocyclic organoboranes

q'l$ isomerization, 43131-134 Heterobimetallic complexes, 32220 lowest unoccupied molecular orbital anal- Heterocarborane ysis, 43127-128 bonding, structural relationship, NMR, 43135-136 3O:lOO-103 reactions geometry, closo polyhedra, 30102 cycloaddition reactions of r)'-com- Group 2 element, 30104-105 plexes Group 13 element, 30105-116 conjugated dienes, 43A79-181 Group 14 element, 30:116-140 diazoalkanes, 43187 Group 15 element, 30:140-147 electron-rich alkynes, 43181-185 Group 16 element, 30147 vinyl ethers, 43185-187 main group, 30:99-150 electrophiles, 43173-175 stability, 30103 insertion reactions, a188 structural nomenclature, 30103-104 nucleophiles, 43175-177 Heterocycles, inorganic, 9329-348 oxidation and reduction, 43177 aluminophosphinimides, 9333-334 rearrangement and displacement reac- cationic isosteres, 9335-337 tions, 43177-179 aluminosiloxanes, 9331 replacement of coordinated ligand by het- aluminosilthianes, 9333 erocarbonyl compound E=C(R')R2, aluminum phosphinates, 9345 43:140-147 aluminum sulfoximides, 9:347 stability, 43125-126 cyclosilazanes, 9329 stabilization by transition metals, 43:126 cationic isosteres, 9337-338 structure, bond lengths and angles, dialkyl-Group I11 hydroxides, 934-345 43~136-138,140 diorganoaluminum fluorides, 9344 synthesis diorganogermoxanes, 9343 complexes with m heterocarbonyl, diorganosiloxanes, 9:342 E=C bond bridging two metal cen- gallium phosphinates, 9346 ters, 43166-172 gallogermoxanes, 9333 heterocarbonyl precursors and metal phosphonitrilic systems, 9341 complexes in synthesis, 43147- silicon sulfdiimides, 9347 148,150-151 silylated phosphorus ylids, 9339 thermochromic behavior, 43136 Heterocycles, thermal decomposition, transformation of coordinated ligand into 44A53-156 heterocarbonyl ligand Heterocyclic aromatics, addition of Grig- alkyl ligands, 43151-154 nard reagents, k232-235 carbene and vinylidene ligands, Heterocyclic compounds 43155-160 arsenic carbyne ligands, 43160, 162 preparation, 4151-152, 154, 159-160, miscellaneous ligands, 43164-166 165-168, 170 thiocarbonyl ligands, 43162-163 reactions, 4173-177, 179, 181, 196-197 thiolato ligands, 43163-164 metallo-ring systems, 5122-124 Heteroallenyl ligand, 3271 a-bonded, 10:138 Heteroarenedicarboxylates, metal, thermal, sulfur systems decarboxylation, 25257-263 reactions, 526, 28, 30-33, 35-37 Heteroatom abstraction, computer represen- synthesis, 54-7, 15 tation, 26194 Heterocyclic organoboranes Heteroatom-carbon, triple bonding, physical properties, 2298-299 44A91-192 reaction with alkylating agents, 2301-303 Heteroatomic anionic rearrangements, 163 with organometallics, 2297 Heterobenzenes, 39325, 336 ring expansion, 2301-303 Heterocyclic organoboranes 134

with two or more B atoms, 2318-321 thermodynamics, 42365-366 Heterocycloalkenes. 13146-1 59 a-Heterodiazoalkanes, 9397-429 reactions, 13156-159 chemical properties, 9410-415 Heterocyclobutenes, 13149- I SO as 1,3-dipoles,9412 of silicon, 13149-150 as electrophiles, 9:412 ring cleavage, 13150, 158 as nucleophilcs, 9411 Heterocyclodienes, 13159-173 physical properties, 9405, 410 cycloheptadiene derivatives, 13164-165, preparation, 9399-405 167 tabulated data, 9406-409 cyclohexadiene derivatives, 13164-166 Heterodienes, reaction with disilcnes, cyclopentadiene derivatives, 13160-163 39261-262 via ring formation reactions, Heterogeneous catalysis 13160-161 of Fischer-Tropsch reaction, 17:62 from saturated heterocycles, 13161 of hydroformylation, 1247-53 transition metal carbonyl complexes, Heteroketone transition metal complexes 13173,255-256 bonding configurations and interactions, rcactions 43128-131 at heteroatom, 13165-169 highest occupied molecular orbital analy- of multiple bonds, 13169-173 sis, 43127-128 Heterocycloheptatriencs, 13191-193 IR spectroscopy, 43135 aluminum, 13192-193 ligand dynamics boron, 13192 q'-E/q'-Z isomerization, 43:134 tin, 13192 q'I$ isomerization, 43131-134 Hctcrocyclohexenes, 13150-156 lowest unoccupied molecular orbital anal- Heterocyclopentenes, 13150-256 ysis, 43127-128 germanium NMR, 43:135-136 free radical bromination, 13158 reactions reactions of multiple bond, 13:158-159 cycloaddition reactions of ?'-corn- reaction with Grignards, 13157 plexes silicon conjugated dimes, 43179-181 free radical bromination, 13158 diazoalkanes, 43187 reduction reactions, 13157 electron-rich alkynes, 43181 -185 substitution reactions, 13157 vinyl ethers, 43185-187 synthesis, 13152-153 electrophiles, 43173-175 Heterocyclopropane, 39:217 insertion reactions, 431 88 Heterocyclopropenes, 13146-149 nucleophiles, 43175-177 boron, 13:148-149 oxidation and reduction, 4k177 dimeric naturc of germanium and silicon rearrangement and displacement reac- species, 13147-148 tions, 43:177-179 phosphorus, 13148 stability, 43125-126 Heterocyclotrienes stabilization by transition metals, 43126 reactions, 13175-176 structure, bond lengths and angles, synthesis, 13173-175 43136, 139-140 Hctcrocymantrenes, 39333, 349-350 synthesis Heterodehydrocoupling complexes with m heterocarbonyl E=C B-WE-H coupling, 42:389 bond bridging two metal centers, heavy elements, 42399-400 43166-172 Si-HIH-C coupling, 42397-399 heterocarbonyl precursors and mctal Si-H/H-N coupling, 42392-397 complexes in synthesis, 43147- Si-HIH-O coupling, 42389-392 148, 150-151 135 Hexachlorodisilane

replacement of coordinated ligand with no ligands attached to Group IB by heterocarbonyl compound metals, 29324-331 E=C(R')R, 43140-147 with one ML fragment, 29260-275 thermochromic behavior, 43136 with three ML fragments, 29293-297 transformation of coordinated ligand with two ML fragments, 29:275-293 into heterocarbonyl ligand synthesis alkyl ligands, 43:151-154 with ligands other than simple two-elec- carbene and vinylidene ligands, tron donors attached to Group IB 43155-160 metals, 29331 carbyne ligands, 43160, 162 with no ligands attached to Group IB miscellaneous ligands, 43164-166 metals, 29324 thiocarbonyl ligands, 43162-163 with one or more ML fragments thiolato ligands, 43163-164 mixed, 29257-259 Heteroles using anionic precursors, 29250-254 molecular structure, 39336 using neutral precursors, 29:254-257 synthesis, 39:327-331 Heteronuclear complexes, of Pt(I1) and Heterolyl rings, 39336-337 Pd( 11) perhalophenyl complexes, 28:252-254 Heterolytic decarboxylation, mechanisms NMR for, 252239-242 Heteronuclear spectroscopy, J-re- 28:432-435 Heteronuclear clusters solved two-dimensional, Heteroscalar correlated NMR spectroscopy, characterization, 29299, 302-307 two-dimensional, heteronuclear correla- chemical properties tion using 'J(X,'H), 28435-440 cleavage of M-P bonds, 29311 Heterosilazanes, aluminum, 9317 cleavage of ML units, 29308 Heterosiloxanes, 9:302-308 Group IB metal exchange reactions, Group 111 derivatives, 9303 29308-310 Group IV derivatives, 9303 homogeneous catalysis, 2931 1 ionic derivatives, 9305-308 29311 ligand addition and substitution, Heterosilylamines, 9317 29310 loss of carbon monoxide, Hexaarylcyclotrigermanes, in digemene 29311 protonation and deprotonation, synthesis, a129 supported Group IB metal, hetero- Hexaarylcyclotrigermanes, photolysis, nuclear clusters, 29312 39287 dynamic behavior Hexabenzyldistannane, 38:198,200 fluxional decapping of M(PR3) moi- Hexa (t-butyl) distannane, 38198 eties, 29321-322 Hexacarbonylbis( ~$-methylcyclo- involving ligands attached to Group IB pentadienyl)dimolybdenum, metals, 29322-323 reactions with conjugated dienes, involving ligands attached to other tran- 26347-348 sition metals, 29323-324 Hexacarbonylbis( $-methylcyclo- metal core rearrangements, 29:312-321 pentadienyl)tungsten, reactions with fast atom bombardment mass spectrome- dienes, 26351-352 try, 29:304-305 Hexacarbonylchromium, 26298-299, Group IB, 29250 316 structures Hexacarbonyl-p-$ CH:~:CH-~,~,~,S- with ligands other than simple two-elec- tetramethyl-2,5-hexadiene-1,4- tron donors attached to Group IB diyldimanganese, 26364 metals, 29331-336 Hexacarbonyltungsten, 26299 with more than three ML fragments, Hexachlorodisilane, silyene-Lewis base com- 29297-301 plex synthesis, 4329, 33 136

(E,E)-ZA-Hexadiene. in photochemical reac- Hexakis(trimethylsilyl)disilane, 3828-29 tions of metal carbonyl complexes Hexakis(trimethylsilyl)ferrocene, 33340 of chromium, 26:298, 325-327, 329 Hexakis(trimethylsilyl)magnesocene, 33340 with decacarbonyldimanganese, Hexamesitylcyclotrigermane, thermolysis, 26:354-358 39287, 300 of molybdenum, M:299 Hexamesitylsiladigermirane, 39287 (E,Z)-2,3-Hcxadiene, in photochemical reac- , 29173, 175, 186 tions of metal carbonyl complexes Hexamethylbenzene cyclohexadienyl ruthe- of chromium, 26:316 nium complexes, 29212 with decacarhonyldimanganesc, Hexamethylhenzene ruthenium(I1) com- 26:354-355 plexes, 29:217-219 Hexa-l$diene, via nickel catalyzed addi- Hexamethylborazene, reaction with chro- tion of ethylene to butadiene, 13307 mium atoms, 1576 2,4-Hexadiene Hexamethyl-1,4-disilabenzene,39150 dodecarbonyl triruthenium reaction, Hexamethyldisilazane, 39162 3776 Hexamethyldistannane, 38200 reaction with silenes, 39112-113 Hexa(2-methylphenyl)distannane, 1,4-Hexadiene synthesis, via catalyzed ethyl- 38196-197 ene-butadiene codimerization, Hexa(4-methylphenyl)distannane, 38196 12271-316 Hexamethylsilacyclopropane, silyenc-Lewis cobalt and iron, 17309-315 base complex synthesis, 4333 nickel, 12291-308 Hexamethylsilirane, reaction with silenes, rhodium, 12271-290 39130 rruns-iosmer from palladium, 12315-316 Hexamethyltrisiloxanc, catalyzed redistribu- (Hcxaethylbenzene)Cr(CO)q, 34297-299 tion, 19238-243 Hexaethyldisilane, 4:3 1,2,3,3a,4,5-Hexaphenyl-S-bora-3a,4- Hexagcrmabenzene. 374 dihydro-5H-benzfe]indene,39:387 Hexagerma-Dewar benzene, 3234 Hexaphenyldilead, structure, 471 Hcxagermaprismane, 321-2, 26-29, 31, 36 Hexaphenyldisilane, cleavage reaction, 384 Hexahydrodiborate ligand, 2k85-87 Hexaphenyldistannane, 38196, 199-200, carbonyliron complexes, 2k85-87 203 Hexakis[bis(trimethylsilyl)methyl]tetra- Hexasilabenzene, 324. 36 cyclo[2.2.0.02~".0'~S]hexagermane,3226 Hexasila-Dewar benzene, 3231-34 Hexakis (2,6-diethylphenyl) cyclotristanane, Hexasilaprismane, 321-2,23-26,36 38:194 theoretical studies, 322-4 Hexakis(2,6-diethylphenyl)cyclotris- Hexastannanes, 38208-21 1 tannane, 3719 Hexa(o-tolyl)disilane, 384 Hexakis(2,6-diethylphenyl)distannane, [HFe,(CO)clNar]-, synthesis, 42121 38194, 197 H,Fe3(CO)sPAuPPh3, structure and bond- Hexakis(2,6-diisopropylphenyI)tetracyclo ing factors, 4240 [2.2.0.02~h.03~']hexagermane,3726-29, HzFe3(C0)9(PR),synthesis, 4284 31, 34 H2Fe,(CO)y(PSiiPr3), synthesis, 4285 Hexakis(2,6-diisopropylphenyl)tetracyclo HFeRu3(CO) I ZN,synthesis, 42117 [2.2.0.0?".0q.~]hexasilane,3%23-27, 31 (Hg(~H,Me~~-2,6)]~.structure, 43293 photochemical reaction, 3731-34 Highest occupied molecular orbital, 33135- Hexakis(2-methylphenyl)distannane, 38203 140,159 Hexakis(2,4,6-triisopropylphenyl)cyclo- diazenes, electronic structure, 3469-70 tristannane, 38194 ketenes, 282 Hexakis(2,4,6-triisopropylphenyl)cyclo- shape of tristannane, photolysis, 39:209 for lithium alkyls, 20294, 296 137 Homogeneous catalysis

for phenoxide anions, 20298-299 by redox condensation, 14:313-314 Highly ordered pyrolytic graphite, 2888 High-pressure liquid chromatography, of High nuclearity metal carbonyl clusters, carbonylhydride clusters, 18248-249 14285-344 Hindered ketones bonding, 14336-341 1,6 addition, k231 analogy with polyboranes, 14337-339 conjugate addition to Grignard reagents, application of noble gas rule, 14336 k228-232 LCAO-MO theories, 14339-341 p-alkylation, k231 topological theories, 14337 (His[(CH2CH2)SiHMe],), synthesis by dehy- cobalt, 14325-327 drocoupling, 42383-384 iridium, 14332-333 (HMB)Cr(CO)L’L” complexes, 34306-310 iron, 14323-324 [(H3N)3Cr(h6-C6Hs-(E)-CH=CHC6H4-4- nickel, 14333-334 NO2)], nonlinear optics, 42353 osmium, 14325 Hofmann acid amide degradation, of car- platinum, 14334-336 bamoylcarbonyl compounds, 18:24-27, reactions 30 effect of core enclosure by carbonyls, HOMO, see Highest occupied molecular or- 14317-318 bital ligand substitution, 14322 Homoallylic alcohols, enantioselective syn- oxidation, 14320-321 thesis using Sn-gr, m.119 oxidative addition, 14:322-323 Homoatomic anionic rearrangements, 16:3 reduction, 14319-320 Homocysteine, methylation by methylcobal- rhodium, 14327-332 amin, 1k426 ruthenium, 14324 Homodehydrocoupling separation, 14:316-317 polygermane synthesis, 42384-385 solid state structures, 14286-306 polyphosphane synthesis, 42:386-387 carbido-carbon radius, 14302 polysilane synthesis of carbido-species, 14300-302 backbone functionalized poly(pheny1si- effect of charge on bond lengths, lanes), 42382-383 14:295 catalysts, 42368-373 of heptanuclear species, 14299 complex hydrosilanes, 42382 metal coordination numbers, limitations, 42367 14293-295 mechanistic considerations, 42373-379 occurrence of triangular metal arrays, preceramic polymer applications, 14291-292 42383-384 octahedron-trigonal prism transforma- stereoselective dehydropolymerization, tion, 14298-301 42379-381 tendency toward close packing of met- polystannane synthesis, 42385-386 als, 14:305-306 small molecule synthesis, 42387-389 solution state structures, 14306-311 thermodynamics, 42365-366 I3C NMR studies, 14:308-310 Homogeneous catalysis IR studies, 14306-308 with acetylene complexes, 14245-265 synthesis, 1431 1-316 with allene complexes, 14265-278 bond energy considerations, asymmetric catalysis, 3tk179-181 14311-313 chiral sulfonated phosphines, 38179-181 of carbido-complexes, 14314-315 cobalt-cyanide complexes, 38171-172 by condensation reactions, 14311-313 of ethylene glycol synthesis, 17230-83 dependence on CO pressure, of Fischer-Tropsch reaction, 1273-80 14312-313 of H-D exchange in alkanes, by pyrolysis, 14313-315 15158-177 Homogeneous catalysis 138

by platinum(II), 15165-174 mechanism, 1k300-302 of hydrocarbon oxidation, 19149 HOMO-LUMO gap of methanol carbonylation, 17:255-267 distibine, 3088-90 supramolecular-medium effects, isoelectronic compound, 30191-199, 205 38~181-182 silane, 30164 tertiary phosphine complexes, 38172-174 HOMO-LUMO interaction diagram, silicon TPPMS complexes, 38174-175 compounds, 33136, 139 TPPTS complexes, 38175-178 Homolytic cleavage TPTS complexes, 38178-179 metal-carbon bond, 38158 transition-metal halides, 38167-171 metal-carbon u-bonds, 7:187 Homogeneous catalysis, relation to oxida- Homolytic decarboxylation, 25242-243 tive-addition reactions, 284-90 Homonuclear dimetal units, clusters of decarbonylation, 7238 dicobaltaboranes, 334-5 hydroformylation, 287-88 Fe2(CO)(,B2H6,333 hydrogenation, R84-87 (715-CSMe5)2Ta2(~-Br2)2(B2HO),332 Homogeneous catalysis, water-soluble li- HMn2(CO)6(B2H6)Mn(C0)4,333-4 gands in Homonuclear NMR spectroscopy, J-re- hydroformylation, 34250-255 solved two-dimensional, 28426-428 cobalt complexes, 34254-255 Homonuclear tetrametal units, clusters of rhodium complexes, 34251 -253 tetracobalt-based, 3330-32 ruthenium complexes, M253 te trairon-based hydrogenation, 34255-270 gold phosphines, reactions with, aqueous phase catalysis, 34259-261 3322-25 asymmetric, 34261-267 [HFe4(C0)12BH]',3322-23, 26 lipids, special application with, HFe4(C0)[*BH2,3318-19, 21 M267-270 HFe4(CO)12CBH2,33:27 two-phase systems, 34255-258 tetranickel-based, 3332 preparation tetraruthenium-based nitrogen-containing ligands, 34233-234 HRU4( CO), 2BH2,3327-28 phosphine ligands, 34:220-233 isoelectronic Ru,E clusters, 3329-30 studies, miscellaneous Homonuclear trimetal units, clusters of carbonylations, 34272-273 tricobalt-based oxidations, 34274 C-0 bond, 335 photocatalytic reactions, 34277-278 Co,(CO)qBNEt,, 3316-17 substitutions, 34274-275 geometry, 3318 support immobilization, M275-277 reaction conditions, 3317 telomerization, 34:273 triiron-based unsaturated compounds, addition to, borirene ligand, 3316 34270-272 Fe(CO)s, reactions of, 338 transition metal complexes Fe(CO), and Bh3 fragments, condensa- non-phosphorus ligands, 34242-245 tion of, 336 phosphine ligands, 34234-242 Fe3(C0)9platform, 337 water-gas shift catalysis, 34245-250 (HFe3(CO)9BH3J-,338 rhodium complexes, 34246-248 HFel(CO)oBH4, 336 ruthenium complexes, 34:249-250 HFe2(CO),nBH2,339 Homogeneous hydrogenation, catalyzed by NMR data, 337-8 pentacyanocobaltate, 11:433 triosmium-based mechanism, 1k435 H,Osq(CO)gBCO, 3310-11 Homogeneous hydrosilylation, transition H,OS,( CO)gCBCI2,3312-13 metal catalyzed, 1k297-310 H3Os,q(CO)&CH2,3313-14 139 Hydride complexes

triruthenium-based HRu6(9-p4-CO)(C0)13(p~-C6H,Me2CH2- BH fragments, Ru(C0)3 substitution 1,3,5), synthesis and structure, 4396-97 for, 3315 1,3-(H&C6H4, dehydrocoupling for poly- HRu~(CO)gB2H5, 3314- 15 merization, 42382 HRu3(CO)lo(mCOBH2NMe3), 335 Hiickel calculations, 154-5, 11 HOMO orbitals, fullerenes, 3668 on bisarene metal complexes, 1354 Homoscalar-correlated NMR spectroscopy, of bonding capabilities of metal carbonyl two-dimensional,2tk428-430 fragments, 1513-14 4,5-Hornotropilidene,37:268 on cyclopentadienylmanganese deriva- H30s3(CO)yBi,synthesis, 4296 tives, 15312 HOs3(CO)&-HN3Ph), synthesis, 4283 on electron-deficient main group com- HOS~(CO),~N,structure and bonding fac- pounds, 15237 tors, 4238 and ESR spectra of Group IVB radical HOS~(CO)~~(PH~),synthesis, 4285 anions, 15298-303 [HP,(M(C0),)]2-,synthesis, 4287 on phosphorus ylides, 14212 [ HRh 1 2(CO)2,(N),]3-, synthesis, 42111 Hiickel methods, nonlinear optics, 4231 1 HRu6C(C0)1s(CCPh), synthesis, 4364 Hiickel molecular orbitals, 26157, 34295- HRu5C(C0),4}2(C204),synthesis, 4359 297,312-315,318 HRU~C(CO)~,~(~-C~H~)~,synthesis, 4372 HX protonations, 35152-157 HRusC(C0) ,3(q-C~H5),synthesis, 4372 Hybridization HRu6C(C0)14($5Me5), synthesis, 4372 in metal olefin complexes, 1521-23 HRu,C( CO)l31 pL-CSH4N) (CsH5N), synthesis and MO theory, 1521-23 and structure, 4386-87 Hydrazine, reaction with rhenium com- HRU~C(CO),~(~-PP~~),synthesis and struc- pounds, 10117 ture, 4356-57 Hydrazinocarbene complexes, synthesis, HRU~C(CO)~,(~-P(P~)CH~CH~S~(O~~)~],4k211-212 synthesis, 4357 Hydride abstraction, computer representa- HRU~C(CO)~~(~-S~H),synthesis, 4359 tion, 26:180, 191, 193 HRu5C(C0)&-SEt), synthesis, 4359 Hydride abstraction reactions, 8126-127 HRu6C(CO),,(p.-SEt),, synthesis and struc- from metal hydrides, 8127 ture, 4360 from organic ligands, 8126 HRu5C(CO),,(p-SEt)(PPh,),synthesis and Hydride bridged complexes, 353-5 structure, 4359-60 Hydride carrier, k80 HRu5C(C0)&-SH), synthesis, 4359 Hydride complexes, l2:21-27 HRuSC(C0)13(NO),synthesis, 4353 chromium, 3211 HRU,C(CO)~~(NO),synthesis, 4353 intermediacy in catalysis, 16264-268 H3Ru5C(CO)11(PPh2Me)(p-PPh2),synthe- hydroformylation, 16267-268 sis, 4392 hydrogenation, 16264-266 HRu3(C0)&-NS(O)MePh), synthesis, iridium, 3245-246 4286 manganese, 3213-215, 217 [HRU~(CO)~~(~~-PR)]-,synthesis, 4284 molecular rearrangement of carbonyl clus- [H~u,,(CO)~~(N),]”,structure and bonding ters, 16332-336 factors, 42:38 tetranuclear, 16:333 HRu3(CO),(NS(O)MePh), structure and trinuclear, 16332-333 bonding factors, 4213-14 molybdenum, 3211 H~Ru~(CO)~PP~,synthesis, 4283 nickel, 3247 HdW(C0)12(Pph) osmium, 3236-237 structure and bonding factors, 4223 rhodium, 3244 synthesis, 42116 ruthenium, 3236-237 [HRus(CO)lo(PPh2)(PPh),, synthesis, 4284 tungsten, 3211 Hydride complexes 140

vanadium, 3195-196 by alumina-supported Os3 clusters, P-Hydride elimination, manganesepentacar- 26:63-65 bony1 alkyls, 32192 by free Os, clusters, 2664-65 Hydride ligand, bonding in bimetallic com- by oxide-supported Os3 clusters, plexes, 2216 2663-64 Hydride-metal bonds, ketene insertion, cluster breakdown, 26:64 283-4 by physisorhed OS,(CO)~~,%63 Hydrides by polystyrene-linked clusters, alkyl, 28:330 2663-64 aryl, 28330 by silica-supported Os3 clusters, beryllium, 9241 26:63-65 cyclopentadienyl titanium(III), 9168 by silica-supported Os? clusters on ox- transition metal, 221-50 ide support, 26:64 manganesepentacarbonyl alkyl reac- by surface-supported Ost clusters, tion, 32183-184 26-63-65 rheniumpentacarbonyl alkyl reaction, mobility, 2658-61 32206 one-carbon ligands, 2655-58 Hydrido( 1-alkynyl)carbene complexes, syn- agostically bonded hydrogens, 26.58 thesis, 4k230-231 carbonyl displacement, 2657-58 formation of methylene ligand, Hydrido(areno)ruthenium complexes, from 2655-57 [RuX,(arene), and RuX2(L)(arene), mechanism, 2656 29176- 183 ketene transformation, 2657 Hydridodisilanes, redistribution reactions, methylene coupling to carbonyl, 2657 19226 methylene isomerization, 2657 catalysis by platinum complexes, 19227 synthesis into C2 ligands, 2657 mechanism, 19:227 Hydrocarbon ligands, p-bonded, carbonyl in presence of acetylenes, 19227-229 complexes without, 25319-322 Hydridonickel complexes, as olefin oligo- Hydrocarbon-metal n-complexes, merization catalysts, 12114 10317-321 Hydrido osmium, from osmium(0) interme- Hydrocarbons, bond encrgy, U69-70 diates, 29198-200 Hydrocarbyls, 3293, 100, 117 Hydridoruthenium(I1) derivatives, from ar- Hydrocyanation of olefins, catalysis ene ruthenium(0) complexes, by nickel complexes, 13324-325 29179-180 by palladium complexes, 13324-326 Hydroboration, 3270, 276-278. 11:12-14, Hydroformylation, 121-57 1330 of acyclic olefins, 1215-32 alkenes, 2275 via carbonyl catalysts, 1215-20 cyclic polyolefins, 2278-279 inhibition by branching, 1217 dialkenyl ethers, 2278 I -octene. 17:24-2.5 dienes, 2275-277 via phosphine-modified catalysts, polyolefins, 2275 122 0 - 3 2 Hydrocarbon ligand chemistry, in tri- relative reactivity of olefins, 1215-18 osmium cluster, 26.55-65 catalyst separation, 1246-47 alkyne dimerization and trimerization, cobalt, 1246 2661-63 rhodium, 1246-47 catalysis by Os, clusters, 2663-65 catalyzed by in alkene hydroformylation, 266.5 rhodacarborane, 14183 in alkene hydrogenation, 2665 supported transition metal complexes, in I-alkene isomerization, 2664 l5218-223 141 Hydroformy lation

with cobalt carbonyls, 15218 tertiary phosphine complexes as catalysts, commercial use, 17:2-3 38173-178 alcohols, 17:2-3 of unsaturated ethers and alkenyl ethers, aldehydes, 122 1242-44 of conjugated dienes, 1244-46 of a,P-unsaturated substrates, 1233-42 of cyclic olefins, 17:32 Hydroformylation reactions, 4255, R87-88 effect of CO pressure, 124, 11 aldehydes and alcohols, 6146 on isomer distribution, 1211 catalytic, 6:128 heterogeneous catalysis, 1247-53 epoxides, 6141, 145 comparison with homogeneous, isomerization, 6:124-128 1250-51 mechanisms, 6:122-124, 128 via polymer supports, 1247-53 olefins homogeneous catalysis catalytic, 6128 cobalt, 17:3-53, 75-76 stoichiornetric, 6:122 copper, 1755, 57 orthoformic esters, 6:145 mechanism, 1254-55 product distribution, 6124-128 platinum, 1254-55 substituted olefins, 6:138-141 rhodium, 124-53 Hydroformylation, ruthenium catalyzed ruthenium, 1753-56 alkenes, 32129-139 silver, 1255 allylic alcohol homogeneous catalysis, mechanism, isomeric distribution, 32128 15222-223 kinetics of, 32:127-128 mechanism, 123-10,54-55 products, 32127-128 carbonyl insertion, 17:4-10 reaction conditions, 32127 comparative rate studies, 125 background and CO partial pressure, 124 early catalysts, 32121 dissociative vs. associative, 129-10 importance, 32121 effect of cluster formation, 125-6 linearity, 32121-122 and H2 partial pressure, 124 reaction conditions, 32121-122 infrared studies with phosphine com- Shell process, 32:122 plexes, 1%6-8 cyclohexene involving ruthenium complex catalysts, dinuclear reductive elimination, 32132 1754-55 diso ration, 32131 isomer formation, 124 reaction conditions, 32131 with nucleophilecarbonyl adducts under solvent, importance of, 32132 WSGR conditions, 28198-201 synergism with [Co2(CO),], 32:131 of a-olefins, 1217-19 ethylene, 32:136 propene, 38:175-176 mechanism, 32137-139 role of u-a rearrangement in catalyzed re- fluoroalkenes, 32:131 actions, 16266-268 hex-1-ene mechanism, 16:267-268 heptanal conversion, 32127 secondary products and reactions, nliso ration, 32:126, 130 17:lO-15 optimum conditions, 32126-127 aldol condensation, 1R14 phosphine ligands, 32130 alkane formation, 1212-13 product separation, 32126 isomerization problems, 1210-11, tetradentate EDTA ligand, 32126-127 13-14 8-methoxy-1,6-octadiene,32134 ketone formation, 1213 oct-1-ene of styrene, 17:16 bridged complex, 32:137 technological trends, 1757 catalytic ability, 32124 Hydroformylation 142

CO inhibition, 32125 asymmetric, see Asymmetric hydroge- mechanism, 32125-126 nation nliso ration, 32124-125 by Co2(CO),/H, system, 6:147-151 oct-2-ene, isomerization to, 32126 aldehydes, 6:150 reaction conditions, 32135 olefins, 6:147 oct-2-ene, 32134 of ketenes, 2854-55 pent-1-ene with nickel-graphite, 28:121-122 hexanal conversion, 32122 of nucleophile-carbonyl adducts, 28175- ligand competition, 32123-124 177, 201-203 mechanism, 32123-124 propionaldchyde, 38:178 nliso ration, 32:122-123, 133 tertiary phosphine complexes as catalysts, reaction conditions, 32123, 136 38173-175,178-179 rhodium vs. ruthenium, 32124 Hydrogenation, catalyzed, 12319-390 selectivity, 32933 by arene complexes triphenylphosphine addition, 32123 chromium, 12336 pent-2-ene, 32130 ruthenium, 12332 photochemical promotion, 32140 of aromatic hydrocarbons, 12376-378 propene by alkylcobalt complexes, 12376 mechanism, 32137-139 asymmetric syntheses, 12338-361, nlisn ration, 32129 366-367 reaction conditions, 32:129, 136 catalyst nature, 17:351-353 sclectivity, 32129-1 30 via chiral amide and amine ligands, Hydroformylation, water-soluble ligands 17:357-359 cobalt complexes, 34254-255 via chiral phosphine complexes of rho- rhodium complexes dium, 17:338-356 amphos ligands. 34:251 via chiral sulfoxide ligands, 17:360 L3 ligand, 34251-252 via DIOP complex, 12339 L, ligands, 34:251 L-DOPA synthesis, 12340 monocarboxylated triphenylphosphine, via hydrosilation, 12354-356 34252 via imine reduction, 12353-356 surface active ligands, 34252-253 via ketone reduction, 12353 water gas shift conditions, 34253 via ruthenium complexes, 12356-357 ruthenium complexes, 34253 by cobalt complexes, 12334-335 Hydrogen mechanistic studies, 17:334 addition to metal complexes, 7:67-69 pentacyano anion. 12325,334-335 effect of ligand character, 268 cobaltrhodium carbonyl cluster, 18256 agostic, 26148-149 by cyclopentadienyl complexes oxidative addition of, computer reprcsen- molybdenum, 12335-336 tation, 26:176 rhodium, 12333 Hydrogen abstraction titanium, 12336 intramolccular, by alkyl radical, a81 in Fischer-Tropsch reaction, 12373-375 reactivity, a79 by GIC, 28:107 Hydrogenase via hydrogenases, 12380-381 coupling to photosynthetic systems, by initial hydrosilation, 12337-338 17:381 of carbonyl groups, 17:337 extrusion of iron-sulfur core, 17:380 of imines to amines, 12337-338 ruthenium complexes as models, via iridium complexes, 12333 12380-381 nitrosyl, 12333 Hydrogenation of ketones and aldehydes, 17:334 alkenes, 38171- 172 via cobalt carbonyl, 12334 143 Hydrogen transfer reaction

by manganese carbonyl, 12336 on support, 12372 by metal complexes, 284-87 use of membrane systems, 12367-368 via organonickel complexes, 12235-237 use of molten salts, 17:368 by osmium complexes, 12336-337 and water-gas shift reaction, 12375-376 phase transfer systems, 12368 Hydrogenation, water-soluble ligands photocatalysis, 12378-379 aqueous phase catalysis via carbonyl libilization, 12378 rhodium complexes, 34260-261 by rhodium acetate dimer, 12372 ruthenium complexes, 34259-260 by rhodium phosphine complexes, asymmetric, M.261-267 12321-332 intial rates, 34262 cationic species, 12328-330 ligand influence, M266 dimers, 12323 lipid applications, 34267, 269-270 hydride intermediates, 12322 solvent influence, 34264 mechanistic studies, 12321-323 two-phase asymmetric, 3k267-269 natural product reduction, 12325 two-phase systems phosphole complex, 12330-331 unsaturated aldehydes, 34258 reduction of 1,3-dienes, 12330-331 water-immiscible olefins, M255-258 Schiff base reduction, 12326 Hydrogen-bridged silicon-transition metal &&unsaturated aldehydes, 12332 bonds, 1k290-291 by ruthenium complexes, 17:323-326, Hydrogen complexes 331-332 of iridium, 259, 68 acrylamide, 17:324 of rhodium, 269 and aluminum alkyls, 12327 Hydrogen-deuterium exchange, 38167 cycloalkene deuteration, 17:327 catalyzed by cobalt cyanide complexes, lactone formation, 12326 11:438 nitro compounds, 12326 Hydrogen-deuterium exchange reactions sugars, 12328 of alkanes, 15158-177 water-soluble catalysts, 12328 catalyzed by platinum(II), 15165-174 supported complexes, 12361-367 of alkyl groups, 15174-177 activity relative to homogeneous cata- in benzene ring, 15:158-165 lysts, 12363 catalysis by transition metal complexes, arenechromium species, 12365 15176 and asymmetric synthesis, 12366-367 in coordinated phosphine ligands, chiral supports, 12366 15148-149, 154-156 effect of crosslinking, 17:363 mechanism, 15155-156 effect of solvents, 17:363 via oxidative addition, 15156 effect of support nature, 12362-363 of organic molecules, 15154-155 ESR studies, 12364 via metal-hydrides, 15:155 in prevention of catalyst aggregation, @Hydrogen elimination, in nickel-catalyzed 12363-364 olefin dimerization, 12119-120 of ruthenium, 12365 Hydrogen halides selective reduction by nickel phosphine addition to metal complexes, 270-73 species, 12365 reactions with unsaturated germanium supported transition metal complexes, compounds, 39:291-292 15205-213 Hydrogen migration, in diene-iron carbonyl by transition metal clusters, 12368-376 complex, 1:14-15,42 comparison with surfaces, 12369 in triene complex, k21 nickel isocyanides, 12370 Hydrogenolysis, of transition metal-carbon platinum-tin complex, 12371 u-bonds, 2182 ruthenium carbonyls, 12371 Hydrogen transfer reaction, 875-80 Hydrogen transfer reaction 144

in triene-iron carbonyl complex, k21 in hydrogermylation, 13322-323 Hydrogen transfer from solvents, in hydrosilylation, 13319-321 12381-383 in olefin dimerization, 13313-314 via iridium catalysts, 12383 in olefin hydrocyanation, 13324-326 via molybdenum complexes, 12382 in reaction of butadiene with hydrox- role in formic acid decomposition, 12383 ylic compounds, 13327 Hydrogerrnylation, catalysis by metal com- infrared studies, of palladium-hydrogen plexes, 13322-323 bonds, 13344-345 Hydrolysis insertion of acetylenes, into palladium hy- acylsilanes, 7A21 drogen bonds, 13301-302 alkyl halides, 38:71 'H NMR data, 13344-345 base-initiated, metal-carbon bonds of phosphine cxchange reactions, 13369 acyl complexes, a185 reaction with , 13306 benzene anion radical, 16:200 synthesis his(trimethylsilyl)diazene, 23152-155 via ligand replacement, 13292 diborane, 3273 via metallohydride reduction, dihalides, 298 13278-279 1,3-dithianes, 2105 by oxidative addition of germanes, effect on synthesis of alkylidynetricobalt 13:288 nonacarbonyl complexes, 14101 by protonation, 13286 iminooxosulfuranes, 36188-1 89 Hydroperoxide, k229 mononuclear alkylidyne complexes of Hydroplatinum complexes, 13273-361 tungsten alkoxides, 22328-329 as catalysts silyldiazenes, 23152-155 in hydrogermylation, 13322-323 thioformyls. formyl complexes via, 1267 in hydrosilylation, 13319-322 tin-group 16 element heterocycles, in linear polymerization of acetylenes, 33:199 13303 Hydronickel complexes, 13:273-361 in olefin hydrogenation, 13331-336 as catalysts in olefin isomerization, 13313, 327-328 in addition of secondary amines to hu- in homogeneous hydrogenation tadiene, 13326 of double bonds, 13328-329 in hexadiene synthesis, 13307-311 of methyl linolenate, Ek329-330 in hydrogermylation, 13323 of polyolefinic esters, 13329 in hydrosilylation, 13315-319 of soybean oil methyl ester, 13329-330 in olefin dimerization, 13313 infrared studies, 13276-277, 292-293 in olefin hydrocyanation. 13324-325 correlation between .pt-H and trans ef- in olefin isomerisation, 13311-313 fect, 13336-337 infrared studies, of nickel-hydrogen of platinum-hydrogen bonds, bonds, 13343-344 13345-353 'HNMR data, 13343-344 insertion into platinum-hydrogen bond, synthesis 13293-305 via ligand replacement, 13292 by acetylenes, 13299-305 via metallohydride reduction, by azides, 13:305 13278-279 by carbon disulfide, 13305 via metathetical replacement, 13278 by diazonium salts, 13:305 by protonation, 13286-287 by dienes, 13299 Hydropalladium complexes, 13273-361, by olefins, 13294-297 368-369 'H NMR studies, 13292-293,345-353 as catalysts phosphine derivatives, mass spectra, in hydration of dienes, 13:326 13:354 145 Hydrosilation catalysis

reactions mechanism, 17:429 with bases, 13307 of conjugated dienes, 12441-443 with carbon tetrachloride, 13306 1,4-addition, 12441 with electrophiles, 13305-307 palladium catalysts, 12441-442 with mercury halides, 13306 effect of silane structure, 12434-441 trans influence, 13305-306 on addition to 1-phenyl alkenes, with water, 13306 12435-436 stability of complexes, formed by oxida- on addition to cpalkenyl , tive addition, 13:281 12436 synthesis, 13276-291 using H20,C16, 12439-441 by addition of germanes, 13284-285 enthalpy of ethylene hydrosilation, by addition of silanes, 13283-285 12407-408 by addition of stannanes, 13285 vs. hydrogenation, 12408 by alkyl elimination, W:291 and heterogeneous catalysis, 12408 from hydrazine reduction, 13277 and hydrogenation, 12337-338 by ligand replacement, 13291-292 asymmetric, 12354-356 via metallohydrides, 13277-279423 of carbonyl groups, 12337 via protonic acids, 13279-283 of imines to amines, 12337-338 by replacement reactions, 13287-291 mechanism, 12409,412 via water and alcohols, 13289-291 of cobalt-catalyzed ring closure, 17:416 Hydroplumbation reactions, 2279-289 via nickel complexes, 12429 alkynes, 2281 square planar vs. tetrahedral geometry, cyano-olefins, 2282 12429 isocyanates and isothiocynates, 2285 by platinum complexes mechanism, 2286 alkylcyclohexenes, 12423-425 olefins, 2279 divalent, 12412-413 Hydrosilane, 3986 involvement of oxidative addition, enantiomeric, 386 12412 Hydrosilation, via homogeneous catalysts, ring closure reactions, 12416-419 17:407-445 side reactions of active catalyst, of acetylenes, 12443-445 12419-426 free radical addition, 12444 styrene, 12413 silane vs. isomer distribution, 12443 zero-valent, 12412 asymmetric synthesis using chiral plati- relative rates of addition to ethylene, num complexes, 12427-428, 438 17:431-432 by chloroplatinic acid, 12409-427 catalyst dependence, 12431 acetylenes, 17:443-445 silane dependence, 12432 on cationic resin, 12414-415 by rhodium complexes, 17:432-434 of heterocyclic aminosilanes, asymmetric synthesis, 12434 12432-433 carbene compounds, 12433-434 induction period, 12409-411 dependence on phosphine, 12432-433 nature of active species, 12411-415 by Ziegler-type catalysts, 12430 and olefin isomerization, 17:411 Hydrosilation catalysis of 1,4-pentadiene, 12418 and C/H exchange, 19218-229 reduction to lower-valent platinum, and methyYhydrogen exchange, 17:410-411 19222-223 ring closure of 4-pentenylsilanes, and redistribution reactions, 19214 12416 via silylplatinum complexes, 19251 by cobalt carbonyl, 12417, 420, 428-429 and vinyyhydrogen exchange, 19219-220 of 1-hexene, 12428-429 of vinyltrimethylsilane, 19235 Hydrosilation reactions 146

Hydrosilation reactions, 637 Hyperfine structure, mononegative ions, with CO~(CO)~,13151 2140 Hydrosilyl anions, 3817 Hyper-Rayleigh scattering, measurement of Hydrosilylation, 13314-322,423 organometallic second-order nonlinear Speier’s catalyst for, 11:298 optical properties, 42306-308 Hydrosilylation catalysis hypho-Carboranes by nickel phosphine complexes, compounds, 36:47-48 15117-118 geometrical systematics and electron pair mcchanisrn, 15118 relationships, 36:24, 27 migration of organosilyl groups, Ziegler-Natta polymerization, 36.48 15117-1 18 by rhodacarborane, 14183 I by supported transition metal complexes, 15213-218 Imidate complexes, synthesis, 4k211-212 Hydro( solvo) thermal technique, synthesis Imidoyl, coordinated ligands, electrophilic of metal-carbonyl polychalcogenide addition to, 25135-138 anions, 4k250-252 Imidoyl complexes, 22287 Hydrostannation, k56, 63-65, 67 Imines Hydrostannolysis reaction, 38191, 205, 215, reactions 221 with disilenes, 39:258 Hydroxyalkyne ligand, 2864 with silenes, 39:128 Hydroxycarbenes, 32188 in synthesis of carbonyl compounds, Hydrox ycarbonyls 28100-101 characterization of complexes, transition metal complexes, 1458 28155-159 Iminio(alky1)carbene complexes, synthesis, decarboxylation of, 28:181-182 4k200-201 spectroscopic data, 2fk15.1-155 Iminium ions. as bridging ligands, 20206 structural data, 28150-152 Iminoacyl complexes, 22267-272,276-277 Hydroxycarboxylation, of nucleophilecar- reaction with electrophiles, 22271 bony1 adducts undcr WSGR condi- Iminometal complexes, by isocyanide inser- tion into metal-carbon bonds, 12:71-72 tions, 2fk203-205 Iminooxosulfuranes a-Hydroxycarboxylic acids, in spirocyclic complexes A’Si-silicates iridium, 36185 ligands, 44:240-241 iron, 36182-184 NMR studies, 44:247, 249-251 nickel, 36185-186 synthesis, 44:242-245. 252 osmium. 36:183-184 X-ray diffraction studies, 44:245-246, platinum, 36185-186 252-254 rhodium, 36184-185 Hydroxymethyl complex, synthesis of non- ruthenium, 36183-184 heteroatom-substituted Os, Ir, and Ru coordinated ligands, 36:191-201 carbene (alkylidene) complexes from. coordination modes, 36:180-182 25160-161 coordination reactions, 36187-191 Hydroxymethylidene complexes, 2022 coupling, N196 Hydroxymethylsilylene. 39131 heterocycle syntheses. 36201 Hyperconjugation, 3913. 202 hydrotungstenation, 36192 boracyclopolyenes, 39:358, 374-375 insertion, 36193 Hyperconjugative effects, in silyl substitu- multiple bonds ents, 15304 alkylidynes, %:I99 Hyperfine interaction constant, 2140 carbonyls, 36199-200 147 Infrared spectra

oxides, 36200-201 heterocarborane, 30:112-113 cT-organyls, 36:192-195 manganese compounds, 3961 orthometallation, 36185 methyllithium derivatives, 24394 reactions, 36191-192 mixed alkali metal compounds, 22218- a-coordinated ligands, 36195-197 221,226 electrophiles, 36:189-191 molybdenum n-bonding, 3953 fragmentation, 36187-188 multiple bonding, 392 hydrolysis, 3k188-189 organometallic compounds, 39:3, 6 ligand substitution, X187 phosphides, 3926-27 nucleophiles, 3k189 terphenyl derivatives, a30 oxidation, 36:189 tetraorganodimetallanes, 396-13 spectroscopic studies, 36:186-187 trihalides, insertion into metal-metal structual studies, 36186-187 bonds, 1818 Iminophosphane, reaction with iminosilane, Indium complexes 39174 borane, 2k66 Iminosilane adducts, 39166-171, 177-183 chromium, 3957 Iminosilanes, 39159, 194, 199 cobalt, 3956 preparation, 39160-171 iron, 3955-56 reactions, 39171-183 transition metal, 3948-49, 55 silaamidide salts, 39185-188 Indium, a complexes silaisonitrile, 39188-189 alkyne complexes, X248-249 silanediimines, 39183-185 arene complexes, 26249, 252, 287 silanitrile, 39189-190 cyclopentadienyl complexes, 26249-251 stable, 39163-166, 171-176 dicarbollyl complexes, 26249, 251-252 unstable, 39160-161, 176-177 structures, 26249 Iminyl complexes, 22293 INEPT, see Insensitive nuclei enhanced by INADEQUTE polarization transfer one-dimensional NMR spectroscopy appli- Inert gas configuration, metal carbonyls, cations, 28:419-422 2169-170 two-dimensional NMR spectroscopy appli- Infrared kinetic spectroscopy, 25289-298 cations, 28430-431 CO laser, 25291 Indanes, via orthocyclization of organopo- dinuclear metal carbonyl species, tassium compounds, 16182-183 25307-31 1 Indenyl compounds [CpFe(CO)2]2, 25309-31 1 lanthanides, 9:376-378 Mnz(CO)lo, 25308-309 samarium, 9:376-378 gas phase photochemistry titanium, 9170 Cr(CO)6, 25303-304 Indenylcopper compounds, a228 Fe(CO)j, 25300-303 Indenyllithium complexes, 26222-223 photochemistry of Cr(C0)6 in solution, TMEDA adduct, 2k218, 225 25304-307 Indenylmagnesium bromide, 26236 Cr(C0)j(H)2, 25306 n-Indenylmetal compounds, mass spectra, Cr (CO) (H20), 25307 8:224, 263-264 Cr(CO),(N2), 25807 Indenylmolybdenum complexes, carbonyl in- Cr(C0)5(solvent), 25304-306 sertion, 1k102 Infrared spectra Indium absolute integrated intensities, 10222 amides, 39:18-26 active vibrations in metal carbonyl deriva- arsenides, 3926, 28 tives, 3188-190 bridged electron-deficient compounds, acylmetalloids, 7:107 15244,250-251 alkyl diboranes, 3289 infrared spectra 148

P-ketometalloids, 7:147 Group 4B metallocene dicarbonyls, cyclobutadiene complexes, 41 18 25347-348 of d4 alkyne complexes, 2962-64 heteroaldehyde and heteroketone transi- internal Mo(I1) and W(I1) bisalkyne tion metal complexes, 43135 complexes, 2959 ketenyl complexes, 2855-56 internal Mo(I1) and W(I1) monoalkyne kinetic, see Infrared kinetic spectroscopy complexes, 2947-51 mixed-metal carbonyl clusters, terminal Mo(I1) and W(I1) alkyne com- 18245-246 plexes, 29:44-47 nucleophile-carbonyl complexes, terminal Mo(I1) and W(I1) bisalkyne 28:151-155 complexes, 29:58 pentahalophenyl metal compounds, diboranes, 3289 28:288-293 diene-iron carbonyl complex, 1:s. 10-11 and redistribution reactions, 23100-101 diplumbanes, 471 R~gC(C0)15,43~46 distannanes, 458 R~gC(C0)17.4346 Group IV organosulfur derivatives, 54I silenes, 2510-15,3999-100 heteroannularly substituted ferrocenes, silyene-Lewis base complexes, 4311-12 10104 time-resolved, see Time-resolved IR spec- metal carbonyls, 3187, 10199-233 troscopy solvent effects, 10:211-212 tin doubly bonded compounds, 39308 metal nitrosyl complexes, 7:231-232 trimethylplatinum(1V) compounds, organoarsenic compounds, 4:220-222 27:132 organo-Group IV hydrides, 7:273 Infrared spectroscopy, s-complexes organolithium compounds, 3374-375 instrumentation, k251-252 organotin compounds, 5146-158 measurement in liquid phase, k253 determination of configuration, 5145 in solid state, k253-254 polygermanes, 444 in vapour phase, k252-253 polysilanes, 424-26 Infrared studies pseudohalogen compounds, 5178-179 on acetylene complexes, 14248-251 sulfur dioxide insertion products, 1234 C=C bond length vs. vc-c in olefin com- transition metal alkyls (aryls), 7:170-171 plexes, 1439, 44 Infrared spectroscopy correlation between JPt+, and "pt-H, anionic transition metal hydrides, 13338 m20-22 correlation between "pt-H and trans ef- borabenzene metal complexes, fect, 33336-337 25209-210 on high nuclearity metal carbonyl clus- carbyne complexes of 0s and Ru, 25188 ters, 14306-308 cobalt-alkyne complexes, 4k82, 95. 119 hydrosilation catalysts, 126-8 C,O-bonded carbonyls, 23222-223. metal carhonyl radical anions, 15311-312 246-247 metal-hydrogen stretching frequencies, with alkali metals, 23228-229 13343-353 alkylated compounds, 23250-251 on methyltin halides, 14:64-65, 68-75 binuclear compounds, 23:270, 275 molecular complexes, 1479-91 Group I11 adducts, 23:251-252 Sn-C bond frequencies, 1464-65 lanthanide adducts, 23251-252 structural studies, 1464-65 dihydrogen complexes, 28303 silicon-transition metal bonds, 11:285 germanium double bonded compounds, silylhydroxylamine anions, 1615 39285 solvent dependency of, "pt-H and trans germenes, M121 effect, 13336-337 149 Insertion reactions

variation of vCN in isocyanide complexes, Insertion 1445-46 activated monomers during Ziegler-Natta vibrational assignments for arenemetal tri- polymerization, 18101 carbonyls, 1356 carbon monoxide Inidene analogs, 3961 into 1,3-diborolene ring, 18307-309 [In(Mn(CO),J5]-, structure and bonding fac- into iron-carbon bonds, 18:182-183 tors, 4269 into metal-carbon bond in Fischer- Inorganic ring systems Tropsch reaction, 17:87-88 four-membered, 9:329-340 into metal-hydride bond, 1267-68 six- and eight-membered, 9:340-348 isocyanide into Pd-C6X5bonds, Inorganic sulfide and thiol complexes, reac- 28267-277 tions ketene ligands, 28:44-45 base induced, 3297 ketenes diazo compounds, 3297 into metal-alkyl bonds, 2&4-5 electrophilic addition, 32103 into metal-ligand bonds, 283-4 hydrosulfide ligand, 32102 into metal-hydrogen bonds, 13294-305 insertion acetylenes, l3:299-305 acetylenes, 3299-101 azides, B305 dithiolene complexes, 32100, 102 carbon disulfide, 13305 ethanedithiolato complexes, 32100 diazonium salts, 13305 ethene, 3299-101 olefins, 13294-299 photochemcial activation, 32100 at M-M' bond by Pt(1) and Pd(1) com- ketone addition, 32:98 plexes, 28283-287 MeCo2C= CC02Me, 3298-99 sulfur dioxide into iron-carbon bonds, Michael addition, 3298-99 18156, 180-182 synthesis in synthesis of methylene addition, 3296 ketenyl complexes, 2&58 thioformaldehyde complexes, 3296 nucleophile-carbonyl adducts, 28149 thiolato ligand, 3297, 109 Insertion reactions, 5225-319, 6:129 [W(CO),SH]-, 32102-103 acetylenes, 14251-261 Insect pheromones, by metathesis of unsatu- mechanisms of reactions, 14253-255 rated esters, 12485 into metal-acetylene bonds, 14251 Insensitive nuclei enhanced by polarization into metal-cr-carbon bonds, 14251 transfer, 23:193-218 into metal-chlorine bonds, 14:251 advantages, 23217 into metal-hydrogen bonds, 14251 application to %i NMR spectroscopy, metalococyclization, 14260-261 23~198-208 metalocyclization, 18256-260 methyl-substituted polysilanes, stereochemistry of products, 23198-202 14251-253 signal enhancement, 23203-206, acyl- and alkylcobalt tetracarbonyls, 215-216 4258-265 silanes, 23202-204 aldehydes, 5230,249-251,294-296 siloxanes, 23199-202 alkenes, 5227,237, 258-271 comparison with DEPT, 23206-208 alkyl and aryl isocyanides, 12.71-12 and DEPT spectra, 23:199-200,202 alkynes, 5:227, 237, 258-277 limitations, 23217 with cobalt-carbon bonds, a358 with one-dimensional NMR, 28410-418 allenes, 5227, 275-276 pulse sequences, 23:196-197 allylnickel complexes, 8:40-48 theory, 23209-213 carbenes, 5231, 9415-424 with two-dimensional NMR, 28436-437 with copper-carbon bonds, a230 Insertion reactions 150

carbodiimides, 5228, 243-247, 288-289 carbonylation, 2189-191 carbon dioxide, 5228, 247-248,291, fluoro-olefins, 2193 E73, 22136-153 olefins, 2193 carhon disulfide. 5228, 247-248,291-292, sulfur dioxide, %191 a74 transition metal-carbon cr-bonds, carbon monoxide, 5230-231, 254-257, 12.3 1-77 302-309,11:88-139 ylides, into silacyclobutanes, 14215 carhonyl sulfide, 5228, 247-248.291 zinc carbenoids chlorosulfonyl isocyanates, a75 with carbon-hydrogen bonds, 12101 cobalt-carbon bonds, 1k427 with Group IVB metal-hydrogen diazoalkanes, 9421 bonds, 12102 dih ydridodecacarbonyltriosmium, Intensities of v(C0) bands 2653-55 absolute, 10222 diketene, 5228, 243-247, 290 hydrocarbon metal carbonyls, 10227 general considerations, 5232-236 iron carbonyl derivatives, 10226, 228 Group IVB dihalides, 1275 M(CO)s complexes, 10225 iridium, into B-H bonds, 14181-182 metal carbonyls, 10224 isocyanatcs, 5227, 243-247, 278-287 molybdenum carbonyl phosphine com- isocyanides, 1k28-36, 22267-289 plexes, 10229 isonitriles, 5231, 253-254, 299-301 nickel complexes, 10228 isothiocyanates, 5228, 243-247, 287 polynuclear metal carbonyls, 10230 ketenes, 5228, 243-247, 289 measurement, 10204-208 ketones, 5230, 249-251, 294-296 Bourgin's method, 10207 metal atoms into carbon-halogen bonds, direct integration, 10205 1578-83 Wilson-Wells method, 10206 main group metals, 1579-80 solvent effects, 10211 transition metals, 1580-83 Intercalants, 2890 metals, 5231 Intercalation, 2885, 89-90, see also Graph- nitrene, 5231 ite intercalation compounds nitric oxide, 1272-73 Interligand C-C coupling reactions, of me- nitriles, 5230, 252-253, 298 talla derivatives of b-diketones, nitro and nitroso compounds, 5230, 251- 2560-70 252, 297 Internal conversion, y rays, 11:211 nitrogen, l274 Intramolecular coordination, organomagne- nitrogen oxides, 5230, 251-252, 297 sium compounds nonmetals, 5231 polyether and crown ether complexes oxygen, 5230, l274-75 coordination geometry, 32189-190 selenium trioxide, 5230, 248-249. 293 crystallization, 32:189 as source of transition metal-carbon cr- halogen-metal exchange, 32190 bonds, 2165-166 higher coordination state, 32192 sulfur dioxide, 1k428 simple ligand complexes rcversible process centrosymmetry, 32184- 185 with bismuth aryls, 1237 coordination geometry, 32185- 188 with mercury aryls, U37 crystal structure, 32186 sulfur oxide, 5230, 248-249, 293 dimer formation, 32184-185 sulfur trioxide, 1272 ring formation, 32184-185 tetracyanoethylene, 12:71 solvent free, 32184-185 tetrasulfur, E75 Intramolecular coordination systems N-thionylamides, 5229, 247-248, 292 cyclometallation, 3439-48 transition metal alkyls (aryls), 2189-195 iridium(III), 34:43 151 Iridium

ligand types, 3442, 49 calculations for ferrocene, l59 NMR spectra, 3449, 51 correlation with rate of H-D exchange oxidation addition, 3450-51, 53 in alkanes, 15172-173 palladium(II), 3439-42, 46 cyclopentadienylgermanium derivatives, phosphines, 3446-48 26263, 273 platinum(II), 34:41, 43-49 dicyclopentadienyllead complexes, 26273 platinum(IV), 3449-55 for dicyclopentadienylmagnesium com- poly(pyrazo1-1-yl) alkanes, involvement plexes, 26:235 of, 34:39-55 for dicyclopentadienyltin complexes, structural studies, 3452-53 26273 structures, 3440, 44, 47, 54 for monocyclopentadienylberylliums, X-ray studies, 3452 26231 Intramolecular reactions, in dodecacarbonyl- organoarsenic compounds, 4227-228 triosmium, 2647-49 and oxidative addition, 12196 Intramolecular ring-closure reactions, of silenes, 2521 phosphine ligands, 15149-154 Ion-pair annihilation effect of phosphorus substituents, electron-transfer processes, 33101-106 15152-153 nucleophilic addition vs. electron trans- involving alkyl groups, 15150-151 fer, 33101-106 involving aromatic rings, 15151-152 nucleophilic adducts, 3397-98 stability of five-membered rings, 15153 thermal decomposition of, 3399-101 Iodine nucleophilic processes, 33:96-106 and dicyclopentadienyl lead(I1) organic radical dimers, 3398-99 compounds, 19129 Ion pairing oxidative addition to organogold(1) com- in alkali metal organics, 27:184-185 pounds, carbenes, 2059, 64 reaction with in anionic transition metal hydrides, osmium carbonyl clusters, 2230-32 2224-27 rhenium complex carbonyl clusters, Ion pairs, ESR spectra, 2148-152 22176 spectral evidence for, 2145-148, 151 unsaturated germanium compounds, Ir,(CO),(PPh,),(PPh), synthesis, 42113 39:292-293 ci~-[IrH(C0)(PPh~)~(~-S=C(CF~)~.],synthe- Iodine compounds, as oxidizing agents, sis, 43147 4067 Iridium Iodine cyanide, oxidative elimination of carbonyl cations, 8:155-157 manganese pentacarbonyl anion, 1812 carbonyl halides, 3:24&247 Iodine oxidation phosphine complexes, 3244-247 alkylidyne metal complexes, 32260 oxygen adduct, 3245-246 Group VI metals, binuclear decacarbonyl cyclopentadienyl(pentadieny1) cations, dianions, 1816 26:152-153, 156 osmium and ruthenium, 25186 high nuclearity carbonyl clusters, 14287 Iodomethyl diplatinum(II1) complex, structural data, 14288 38162-163 synthesis, 14:332-333 Iodoterphenyl reagents, synthesis, 44:4 mixed metal clusters, 18:220, 224-225, Ion-dipole complexes, of alkali metal organ- 239 ics, 22236-238 tricarbonylmetallate(3-) anion, 3k36-39 Ionicity, of alkali metal organics, in triosmium clusters, 26:78-80 22174-176 Iridium, d6-alkylir'ene complexes, synthesis, Ionization energy, germenes, &121 25159-161 Ionization potentials from carbyne complexes, 25159-160 Iridium 152

from hydroxy-, alkoxy-, and halomethyl antimony and bismuth, 3k148-154 complexes, 25160-161 bimetallic, 32229-230, 232, 256, 262, 277 Iridium, d*-alkylidene complexes, synthesis, boranes, 21:63-66, 68-69, 79, 82, 94, 97, 25156- 159 103- 104 alkylidene formation mechanism, carbonyl diazene, 3498 25158-159 chlorocarbonylbis(phosphine) diazoalkane route, 25156 as disiloxane redistribution, catalyst, reactions with OsC1(NO)(PPh3)3, 19235-247 25156- 157 and silane disproportionation, reactions with other substrate complexes, 19221-222 23157-158 cluster, 30:224 Iridium alkyls, carbonylation, 11:97, 102, C,O-bonded clusters, 23289-290 115-116, 135-137 of copper and acetylenes, Kk285-286 Iridium, carbene complexes dicarbonyl(vinylcyclopentadienyl), bonding models, 25123-125 21:41-42 carbene fragment, 25123 electron-transfer reactions charge distributions, 25124 carbonyl phosphine halides, 2331-32 coordination to metal, 25:123-124 dienes, 23:40-41 geometries, 25124- 125 phosphine hydrides, 2331 substituent effects, 25124 pyrazolyl-bridged compounds, a123 reactivity patterns, 25125-129 thiolato-bridged trinuclear carbonyl, effect of metal basicity, 25127-128 x120 reactions with nucleophiles, 25126-127 formyls, 207, 10 Iridium, carbyne complexes hydrides, 2012-13 bonding models, 25129-131 reduction, 2024 carbene fragment, 25129-130 fullerenes, 3672-75 charge, 25131 iminooxosulfuranes, X185 heteroatomic substituents, 25130 p-methylene cyclooctadiene compound, substituent effects, 25130-131 20191 varying metal fragment, 25131 p-phenylene derivative, 20240 reactivity patterns, 25131-134 N-, 0-,S-, and Se-substituted carbene, electrophilic addition, 25133-134 25142- 146 nucleophilic addition, 25131-133 nitrogen complexes, 284 Iridium complex catalysts in oxidative-addition reactions carbonyl clusters in Fischer-Tropsch reac- acetylenes and olefins, 7:65 tions, 1275, 79 oxygen, 263 with aluminum chloride, 1279 phenylethynyl, 38127-128,132, 137-138 methane formation, 1279 reaction with sulfur dioxide, Kk68 product distribution, 1279 redistribution reactions in hydroformylation, infrared studies, carbonyl phosphine halides, 2396, 17:6-8 107-110, 112-113 in hydrogenation, 12333 hydrides, 23116-117 in methanol carbonylation, 17:264-266 T*-SiH, 30182 Iridium complexes, see also Vaska’s with silyl ligands, 1k259 complex hydrosilylation, 1k303-305 acyl-alkyl rearrangement, 1k110, 115 stereochemistry, 11:115 alkyl halide, 3862 TPPMS, 38175 alkylidene carbaborane, 31:67, 76 lridium, dihalocarbene complexes, synthesis anionic hydride, spectroscopic properties, cation generation for CCl, with silver 275 salts, 25171 153 Iron

CCI2 complexes from reactions with metal-carbon bond of, 25162-163 Hg(CC1,)2, 25170-171 nucleophilic addition reactions, conversion of CC12 complex to CFCl com- 25: 167- 168 plex, 25171 nuclophilic addition to Os(=CH2)- modification of Cl( NO)(PPh3)2, 25167-168 a-dihalocarbene ligand containing com- reactions with halogens, 25167 plex, 25171 reactivity, 25164168 trihalomethyl derivatives, Ln-CX3, spectroscopic properties, 25163-164 25169-170 structure, 25161-164 Iridium, dihalo- and monohalocarbene com- sulfene complex reactions, 25166 plexes synthesis metal-carbon bond, 25173 d*-alkylidene complexes, 25156 metallacycle formation, 25179-180 reactions with OsC1(NO)(PPh3),, migratory insertion reactions, 25180 25156-157 reactions with trans influence, 25163 electrophiles, 25180 Iridium, platinum clusters nucleophiles, 25176-179 crystallographic characterization, 3k340 structure fluxional behavior, 3k319, 321-323 carbene ligand orientation, 25175 raft structure, 31:372-373 carbon-halogen bond, 25173-174 synthesis, 3k303-305, 372 13C NMR, 25175 trinuclear, 3k366-367, 374 IR spectroscopy, 25175-176 Iridium, trimethylenemethane complexes metal-carbon bond, 25173 reactions with trans influence, 25175 nucleophiles, 22296-297 Iridium, isocyanide complexes, 1k65-68, silver hexafluorophosphate, 22299-300 22222-223, 260 tertiary phosphines, 22297-298 cluster carbonyls, 22229 role in organic synthesis, 22306 fluxionality, 22242 structure, 22289-290 oxidative addition reactions, 1k66 synthesis, 22285-286 photochemistry, 22257 Iron Iridium, monohalocarbene complexes, syn- 7i-arene-8-cyclopentadienyl cations, thesis 1044-47 modification of binuclear octacarbonyl dianion carbyne complexes, 25172 insertion reaction with Group IIB met- 0-dihaloalkyl derivatives, L,M-CX2R, als, 1815 25171-172 reaction with tin(1V) compounds, 1818 monohalocarbene ligand-containing bis(ethy1ene)cyclopentadienyl anion, complex, 25172 19:117 oxidative addition of [Me2NCCl2]C1, carbonylation, 19117 25172 cyanocarbonyls, 1838-41 Iridium, nonheteroatom-substituted carbene alkylation, 18:41 (alkylidene) complexes allyls, 1839 carbene ligand conformation, 25163 diene complexes, 18:39-41 chalcoformaldehyde complex reactions, ( v4-cyclooctadiene)(~5-cyclopentadienyl) 25166 compounds, 19117-118 electrophilic addition reactions, anion, 19117 25164-166 paramagnetic neutral complex, 19117 gold adduct reactions, 25166 zinc derivative, 19118 halomethyl ligands as methylene precur- ($-cyclooctadienyl)( 7'-cyclopentadienyl) sors, 25167 compounds, 19118 Iron 154

cyclopentadienyl cobalt and rhodium clus- Iron alkyls, carbonylation, 11:93, 97, 100- ters, 18258 101, 126-130 Mossbauer spectra, 18248 Iron, anionic hydride complexes stereochemical nonrigidity, 18248 as catalyst, 2744-45 dienetricarbonyls reactions, 2228-29 "C NMR spectra, 19:275-277 with acid halides, 2241 phase transfer catalyzed carbene inser- with aldehydes, 2243 tion, 19206-207 with alkyl halides, 27:35-37, 40-41 high nuclearity carbonyl clusters, 14287 with BrGnsted acids, 2232-33 reactions, 14324 with Lewis acids, 27:32-33 structural studies, 14288, 290, 293 with small electrophiles, 2234 mixed alkali metal compounds, 22246- spectroscopic properties, 2R4-5, 7, 20- 250, 256 21, 23-24, 26-27 mixed-metal clusters, 18210-220 structure, 229, 15-17 nitrido clusters, 21.50, 52-53, 62-64, 66, Iron, borane complexes, 2k63-69, 73-75, 70-72.75-76, 78 95,97-98, 102-103 with ruthenium, M56, 63, 68-71, 73, hexacarbonyldiborane, 21:85-87 75, 77, 80 interstitial compounds, 2k101-102 nitrosylcarbonyls, 24:43, 47, 55 multinuclear compounds, 2k96-98 organogallium compounds, 3948-49, "B NMR spectra, 2k82-83 51-53 tricarbonyltetraborane, 2k61, 77-82, 104 organolithium derivatives Iron carbidocarbonyl clusters, 223-17, 53 cyclooctadiene cyclopentadienyl, carbide carbon chemical shifts, 2247 effective radius of carbide carbon, 2250 X401-402 hexanuclear hexadccacarbonyl dianion, of ethylene, 24399-400 223-4 of fcrrocenyl group, 24402-405 carbomethoxymethylidyne derivative, organotin(I1) derivatives, 19145-147 22:6-7 osmium and ruthenium carbonyl clusters, ferric ion oxidation, 223, 5 18215-21 6 structure, 224 analysis by mass spectrometry, 18244 tropylium bromide oxidation, 226, 14 synthesis, 18228 pentanuclear pentadecacarbonyl, 223 reaction with alkyl halides, 3873 pentanuclear tetradecacarbonyl dianion, silametallacyclopentane. 19216 223 tetrakis(ethy1ene)dilithium compound degradation of metal complex adducts, carbonylation, 19:119 22s structure, 19119 mixed metal derivatives, 225-6 tricarbonylnitrosyl anion, 2226 reaction with metal complexes, 223-4, derivatives, 2:227-228 189 Iron, acyclic pentadienylmetal complexcs, pentanuclear tridecacarbonyl dibromide 26136-137, 139-141, 143-147 dianion, 2214 bonding parameters, 26139-140 size reduction by oxidation, 22194 conformation, 26140 tetranuclear dodecacarbonyl dianion, molecular orbitals, 26157-158 229-1 I oxidation potentials, 26:158 oxidation under hydrogen, 2210-11 B complexes, analogy to carbocations, reaction with metal carbonyl anions, 26257 22188-189 77'-pentadienyltricarbonyliron cations, structure, 2210 26: I 43- 147 tctranuclear tridecacarbonyl, 228-9 substituted tricarbonyl complexes, 26323 phosphine derivatives, 228-9 Iron complexes

reduction, 229 P-chlorovinyl ketone complexes, 1032 Iron carbonyl anions, 1:37-38,2218-226 ethylenediamine complex, 84 alkyltin derivatives, 2224 mass spectra, 6275, 278-279 alkyne derivatives, 2222-223 in phase transfer catalysis, 19185 chalkogen derivatives, 2225-226 effect of CO, 19:187 lead derivatives, 2224-225 intermediacy of carbonylates, 19185- mercury derivatives, 2224 186, 188 metalloid derivatives, 2226 ketones from halides, 19188 perfluoroalkyl derivatives, 2222 reduction of a&-diketones, 19189 preparation, 2218-221 reduction of nitrobenzenes, 19185-187 properties, 2221 phosphine derivatives, 85 Iron carbonyl complexes, 3224-235, 1k60 reactions with cyclopentadienyl derivatives, 3234-235 ammonia, 1820-21 halide complexes, 3230-232 diaryldiazomethanes, 9429 kinetics and mechanism of reactions, structural data on nitrogen-bridged, 1k94 10120 nitrosyl complexes, 3229-230 Iron, carbyne complexes olefin complexes, 3233 reactions phosphine complexes, 3224-226, 232, carbyne coupling, 2285 234-235 with nucleophiles, 2277 protonation, 3225 structure, 2R55 reactions with Lewis bases, 3224-229 synthesis, 2758 sulfur derivatives, 3226-229, 239 Iron, chiral cyclopentadienyl carbonyl phos- vinyl sulfide complex, 337 phine complexes Iron carbonyl diazene complexes carbonylation of alkyls, 18182 aryldiazenes, 3474-75 circular dichroism, 18171 bisdiazenes, 3475 decarbonylation of acyls, 18182-183 cyclic diazenes, 3475-76 diastereoisomeric enantiomers, Fenske-Hall model, 3476 18189-191 IR spectrum, 3473 electrophilic cleavage of iron-ligand Mossbauer studies, 3k73-74,77-78 bonds, 18183-185 NMR studies, 3473, 75, 78-79 epimerization and racemization, 18:177, oxidation, 3480 185 preparation, 3472, 74-75, 78-79 ligand transfer and configuration at iron, structural parameters, 3474 18 170- 172 substitution chemistry, 3480 optical resolution a1 alkyls, 18156-157 uv-vis spectrum, 3474 sulfur dioxide insertion, 18156, 180-182 X-ray crystallography, 34:73, 75-76, 78 Iron complexes Iron carbonyl diazirine complexes, 3472, 80 p-alkanediyls, 2&238-239 bond cleavage, 34:95,97-98 alkyl, 38108, 110 IR analysis, 3496-97 alkylidene carbaborane, 3k71-74 Iron carbonyl-diene carboxylic acids, pK, alkynyl, 3883-84, 89, 99, 104, 108, 110, values, k13 115, 119-120 Iron carbonyl halide, 813-14 allenyl, 3289, 118 Iron carbonyl hydride, 86 ally1 tricarbonyl halides, NMR studies, Iron carbonyl nitrosyl, 810-11, 21-22 16219 cationic derivatives, 8145 arene, 1%65,78-79,93-102 Iron carbonyls, 82 assisted carbonyl insertion reactions in alkane solutions, effects of ultrasound by amphoteric molecules, 23286-287 on, 2595 by cations, 23281-282 Iron complexes 156

of cyclic polyolefin complexes, 21285 diiron bridging methylidyne, 3267-68 by Lewis acids, 23283, 287 dinitrogen as hydrogenation catalyst, bimetallic, 32224, 228-229, 231-232, 234, 12331 240,243,250-251,253, 257-269, edge-bridged Z-C,O-bonded carbonyls 275-276,280-288,290-293.297-298, alkylated clusters, 23249-251 300,308 on alumina, 23256 binuclear carbon-bridged porphyrin, cluster hydride, 23246-247 2215-17 Group I11 derivatives, 23251-252, 254 bis(cyc1ooctadiene)dilithium. 19119-120 lanthanide derivatives, 23251,254-255 y-l,3-butadiene-l ,4-diyl, 20239 face-bridged Z-C,O-bonded carbonyls calculations on dienetricarbonyls, acyls and alkyls, 23264-266 1527-30 with Group I11 acceptors, 23:260-264 carbamoyl cyclopentadienyl, 1828-29, 32 fluxional polyene tricarbonyls, carbene, 144, 7 16:234-236 in carbon dioxide reduction, 22157 formyl in Fischer-Tropsch reaction, carbonyl-bridged ytterbium, 24166-167 1267-68 carbonyl cleavage or reductions reac- formyls, 205, 7-9, 18 tions, 23288-291 decomposition, 20:26 carbonyl redistribution reactions, 23103, and ketone reduction, 2017 105-106, 109-112 protonation, 2021-22 catalysts of ethylene-butadiene codimeri- fullerenes, 36:76-77 zation, 12309-315 7'-heptafluorocyclooctatetraenyl $-CH, 30183 crystallographic study, 3k248-250 clusters, 22171-176 ligand substitution, 3k250-251 anion, 30:235 synthesis, 3k247-248 electronic structure, 30226-228 heterocarborane, 30:144 hydrogen, M234-235 hydridotetracarbonyl anion, ion pairing protonation of carbonyls, 22174-175 and CO dissociation rate, 2k122 reaction with nucleophiles, 22176 iminooxosulfuranes, 36182-184 redox chemistry, 22171-173 indium, 3955-56 copper and acetylenes, 12:286-287 with isocyanides, 1k58-61 7'-cyclooctatetraenyl, 3k245-255 reactions with nucleophiles, 1k37-39 cyclopentadienyl dicarbonyl dimer, isoelectronic, 30204-207, 209-21 1 16:323 main group carbonyl exchange, 16:323 antimony and bismuth, 31:139-147 I3C NMR spectra, 16319-320, 323 gallium, indium, and thallium, cyclopentadienyls 3k101-106 with cyanovinyl substituents, 2k44-45 germanium, tin, and lead, 31:117-122 halo-substituted, 2k24-25 indium mixed metal, 3k99-101 on polymer support, 2k47 tellurium, 3k165-167, 169-174 1,4-diaza-1,3-butadienes mass spectra, 8259-271 bridged hexacarbonyl, 21:158, 162-163, ferrocenes, 8241-259 193-1YY via metal atom synthesis, 1595-96 chelated compounds, 2k160-161, of 1,3-butadiene, 1568-69 178-181 of cyclooctadienes, 1567-68 as dime polymerization catalysts, methylidene, 32231 2k233 molecular rearrangements ligand activation, 21:217-221, 227-228 of dinuclear olefin species, 16:336-338 dicarbonyldinitrosyl substitution, effect of of hydride carbonyl anions, 16333 hydroxide ion, 2k138-139 I3C NMR spectra 157 Iron complexes

carbonyls, 12:176, 191 as Ziegler-type hydrosilation catalysts, 7i-cyclopentadienyls, 12:148, 155, 187 17:430 dienetricarbonyls, l2:154 Iron complexes, electron-transfer reactions fluxional molecules, 12:148 $-alkenes, 2336-37 octafluorocycloocta-l,3,5,7-tetraene, alkyls, 2335 3k211-213 and metal-carbon bond cleavage, 2335 olefin, via ferrocene reduction, $-allyls, 2337 19117-118 arenes pentacarbonyl derivatives, substitution cyclopentadienyl cations, 2492 mechanism, 21:125 fulvalenes, 2492 perfluoro-l,3-diene, 3k197-198 bis(fulva1ene) dimer, X89-90, 122 perfluorotricyclo[4.2.0.0]octa-3,7-diene, carbenes, 2327-28 3k214-217 carbonyl phosphines, 2325-27 phenylethynyl, 38123-124, 134-136 oxidative addition, 2325-26 polynuclear cyclooctatetraene, 19180 silver(1) adducts, 23:25 polynuclear n-C,O-bonded clusters, carbonyls, 2324-25 23276-279 carboranes, 24.96 acyls, 23:278-279 clusters, X112-116 heteronuclear, 23276-278 of mixed metals, X121, 124 polynuclear species, I3C NMR spectra, phosphorus-bridged cobalt carbonyl, 16320-322 M113 porphyrin dioxygen complex, 16:274 sulfur-bridged carbonyls, 24:114 reactions with sulfur-rich tetranuclear species, 24116 trinuclear carbonyls, 24:112-113 bis(trimethylsilyl)diazene, 23186-187 cubane derivatives, X114-116 isocyanides, 1k35 photooxidation, X11.5 $-SiH, 30180-182,207-208 structure and bonding, 24114-116 silacyclopentadiene, 13173 cyclooctatetraene, 2340-41 silyl derivatives, 11:256 oxidative dimerization, 2340-41 terminal C-C, 0-bonded carbonyls cyclopentadienyl arenes, 2371-74 with alkali metals, 23230-234 acyl group reductions, 2372 cluster hydride, 23228 C-H bond activation, 2373-74 cyclopentadienyls, 23220, 224 reduction to cyclohexadienyls, 23:71 with magnesium ions, 23235-237 reductive dimerization, 2372-73 X-ray structures, 23231-234 cyclopentadienyl carbonyls, 2352-57 tetracarbonyl, k14, 35-36 acyl formation, 2356 p-tetraff uoroethylene, 20240-241 alkyl cleavage, 2355, 78 tetranuclear dodecacarbonyl carbometh- ally1 dimerization, 23:56-57 oxymethylidyne anion, 226-7, 13 isocyanides, 2353 mechanism of formation, 22:14 thiolate dimerization, 2353-54 protonation, 228 dienes, 2338-41 synthesis, 2215 cyclobutadienes, 2339 tetranuclear hydrido methylidyne, 2210- ferroles, 2338 11,13 ferrocene derivatives, 2369-70,78 fluxionality, 2211 ferrocenophanes, X89-YO, 92 thallium, 3959-60 ferrocenyl derivatives trimetallic, 3Z246, 269, 276, 298 of boron, X91 p-vinylcarbene, 20219-220 of carbyne-bridged cobalt cluster, reversible decarbonylation, 20219 24118, 124 structure, 20220 of cyclobutadiene cobalt, 2491 Iron complexes

isocyanides, 2327 isomerism, 20190-191 ligand-bridged bimetallics, 24:100-101, reactions with hydrogen and ethylene, 103-105 2k222-223,229 carbonyls, M101, 104-105, 122 tricarbonylbis(cyclopentadienyl), 20168, cyclopcntadienyls, 24105-106, 122 182-183 metallacycle, 24:106 trinuclear anion, 20251 phosphido-bridged nitrosyl, 24104 X-ray structural data, 20233 mediation by CO ligand, 23293-296 Iron, nitrosyl clusters nitrosyls, 2328 carbide, 2444, 46, 51-53 polyferrocenes, 2489, 91-92, 122 mixed metal derivatives, 2448-54, 56-57, vinylferrocene polymers, 2490 63 Iron complexes, photochemistry nitride, 2450, 62-63 binuclear alkylidene-bridged carbonyl sulfide, 2445.48-49, 51-54 cyclopentadienyls, 24339-340 Iron, osmium and ruthenium carbonylhy- alkyne insertion, 24339-340 dride clusters, 18217-219 dicarbonyl cyclopentadienyl acyls, carbonylation, 18217-219 24299-300 carbonyl substitution, 18208, 252 o-metallation reaction, 24299-300 as catalysts for water-gas shift reaction, dicarbonyl cyclopentadienyl alkyls. 18256-257 24293-299 deprotonation, 18253 acyl formation, 24294 electronic spectra, 18246 alkyne insertion, 24294 hydrogenation, 18255 carbonyl insertion, 24:293-295, 298 IR spectra, 18245-246 in CO matrur, 24297-298 mass spectra, 18242-244 hydride formation, 24294, 296 reaction with alkynes, 18255 tetracarbonyl azo complex, 24292-293 tri(isopropy1) derivative, 24292 stereochemical nonrigidity, 18261-264 Iron dicobaltnonacarbonylsulfide, 18215 synthesis, 18235-236, 241 carbonyl substitution, 18250-253 Iron platinum clusters, 3k328-383 as donor ligand, 18252-253 chalcogenide stereochemical nonrigidity, 18258-259 structure, 3k346 synthesis, 18228-229 synthesis, 3k346 Iron-graphite, 28123-124 crystallographically characterized, Iron isocyanides 3k330-331 carbonyls, 22226, 228-229 fluxional behavior, 3k322 cyclopentadienyls, 22218-219, 229-231. high nuclearity 245, 257 bow-tie anion, 3k344 and alkyl halides, 22294 "Fe MBssbauer spectroscopy, fluxionality, 22215-216, 239-241 3k344-345 oxidative addition, 22259 planar species, 3k345 protonation, 22293-295 structure, 3k343-344 homoleptic spccies, 22222, 245 synthesis, 3k303-305 porphyrin, 22219, 234 tetranuclear Iron, p-methylene complexes diplatinum species, 3k342-343 dinitrosylbis( cyclopentadienyl), structure, 3k342 20177-179 vinylidene, 3k343 mass spectrum, 20216 trinuclear, 3k329-342 Group IVB analogs, 20231-237 bonding mode, 3k342 hexacarbonyl-p-thiolate, 20194 polarographic study, 3k341 octacarbonyl, 20182 preparation, 3k341-342 159 lsocyanide complexes

Iron silicon carbide ceramics, formation via Isobutene, reactions pyrolysis, 32150-151 with iminosilanes. 39173 Iron, tricarbonyl cycloheptatrienide anion, with silene, 39114 1841-42 Isobutyl rheniumpentacarbonyl, synthesis, and cationic dienyliron compounds, 1842 32176 and chloroformic esters. 1842 Isocarbonyl species, as Be derivative, 44A1 and Group IVB halides, 1842 Isocyanate structure, 1842 properties, 5208-210 synthesis, 1841 reactions with Iron, trimethylenemethane complexes disilenes, 39258 orbital diagram, 22291 metal carbonyls, 10121 reactions, 22299 Isocyanide complexes, 1k21-81, 22209-310 with electrophiles, 22294-295 addition of alkoxide, 11:40, 42 redox reactions, 22298 amines, 1k45 with tertiary phosphines, 22297 hydrazine, 11:43 role in organic synthesis, 22301 addition reactions structure and bonding, 22289-292 with alcohols, 22:289-291 synthesis, 22280-284,287-289 with amines, 22289-291 Iron vinylidenes from carbene complexes and amines, binuclear cyclopentadienyls, 22:78-81, 22218-21 9 103, 108-109 carbene formation with alcohols, 147 cluster formation, 2282 via carbodiimides, 22219 isomerization, 2279 via carbonyl substitution, 22224-231 protonation, 2281 carbyne formation, 22:292-295 binuclear octacarbonyl, 2277, 102, 108, catalyzed reactions, 22225-231 123 phase-transfer catalysis, 22:225 clusters cobalt, 1k63-65 carbonyls, 22117-118, 120, 124 via desulfurization of isothiocyanates, cyclopentadienyls, 22120 22219-220 cyclopentadienyls, 22:63-66, 68-70, 90- via dinitrogen substitution, 22:232-233 91, 94, 100, 104-107 electron-transfer reactions, 236-11, 22- bonding, 22:98 23,27,32,50,53-54 cyclobutenylidene formation, 2274-75 fluxionality, 22239-243 deprotonation, 2273 formation of carbene complexes, 1k40 nucleophilic addition to cations, tetrazole derivatives, 1k41 2211-73 Group VI metal derivatives, 1k49 reaction with alcohols, 2270 homoleptic species, 22210 reduction, 22113 insertion reactions, 22212, 267-289 porphyrins, 2267, 91-93, 106-107 iron, 1k58-61 from DDT, 2267 manganese and rhenium, 1k54-58 electrochemical reduction, 2293 by metal atom synthesis, 1566 reactions, 2292-93 from metal cyanides, 22216-218 Irreducible representations, k244-246, via aldol condensation, 22216-217 249-251,254 alkylation, 22216-218 IR spectroscopy, see Infrared spectroscopy and benzoyl chloride, 22218 Isobenzofuran, reaction with disilenes, chiral synthesis, 22218 39257-258 and diazonium salts, 22217-218 Isobenzothiophenyl-Group 10 metal com- molecular rearrangement of clusters, plexes, third-order nonlinear optics, 16:332 43371,373-374 nickel. 11:68-74 lsocyanide complexes 160

NMR studies, 22238-243 insertion reactions into Pd-C6X5 bonds, nucleophilic reactions, 1k36 28.267-277 in organic synthesis, 22295 organocopper complexes, l2228, 242 oxidative addition, 22220, 259-263 properties, 5182- 186 palladium and platinum, 1k74-80 reaction with 1,3-ditungstacyclobuta- reaction with azides, 1k41 dienes, 26:116-118 redox reactions, 22255-257 Isodiazene, structure, 23:138-139 photochemistry, 22251-259 Isodiazomethane complexes, 22218 rhodium and iridium, 1k65-68 Isodicyclopentadienylthallium, 26:253-254 ruthenium and osmium, 11:60, 62 Isoelectronic cluster, 30218-235 structure and bonding, 1k23, 22213-216, borane, W219-225 233 butterfly anion, 30235 bridging ligands, 22214-215 electron counting, 30223-225 dynamic behavior, 22215-216 model compound, 30:219-223 MO description, 22213-214 skeletal electron counting (Wade’s) rules, substitution reactions, 22251-255 30:218 synthesis, 22220-238 Isoelectronic compound clusters, 22231 definition, 30190-192 homoleptic species, 22220-224 isolobal, 30:191 from thiocarbonyls and amines, 22220 skeletal electron count, 30191 variation of vCN with metal oxidation Fenske-Hall approach, 30192-196,209- state, 14:44-45, 248-251 211, 219-223,227 X-ray structures, 22243-251, 263-267 free ligand, 30:193-195 Isocyanide ligands CO, BO-, and HBO, 30194 addition to acetylide complexes, 22279 HBO and HCN, 30194-195 insertion reactions with metal complexes, NZ,CO, and BF, 30193-194 22261-289 halogen, dipnictogen, 3093-94 acetylenes, 22278 Koopman theorem, 30:197-198 alkyls, 22261-277 metal complex, 30195-199 allyls, 22278 carbonyl, nitrosyl, -195-196 aryls, 22267-277 carbonyl hydride, W196-197 carbenes, 22279-281 orbital correlation, -193-199, 210-211 carbynes, 2281 photoelectron spectroscopy, W197-198 halides, 22289 Si-H-M, 30:207-208 hydrides, 22281-284 reactivity, 30208 with metal-nitrogen bonds, 22284-286 structure, W208 with metal-oxygen bonds, 22286-288 Isoelectronic EM3 cluster vinyls, 22279 BrBnsted acidity, 30:229 synthesis, 22216-220 deprotonation kinetics, 30229 Isocyanides electronic structure, 30:226-228 binuclear metal complex reactions, ESR measurement, -228 28.285-287 UV photoelectron spectroscopy, 30228 coordinated ligands, nucleophilic addition example, 30:222-226 to, 25138-140 hydrogen source, sink, 30233-235 copper-catalyzed additions, 1k47-49 Lewis acidity, -229-231 copper complexes as catalysts, transition metal, 30230-231 l2307-310 Lewis basicity, 30231-233 insertion into metdl-carbOn bonds, 1k28- synthetic consequence, M232 36. l.271-I2 Isoelectronic polyhapto ligand complex, mechanism, 12:72 W208-218 161 KC(SiMe,),

cyclopentadienyl sandwich, 30216 tungsten alkoxides, 22358 dialkyne, diphosphaalkyne, W214-215 Isopentalenethallium, 26:253-254 model, 30209-212 Isoprene monoalkyne, phosphaalkyne, W214-215 cocyclization with arylisocyanates, 12178 early transition metal, W212-216 palladium-catalyzed reactions, 12168-176 triple-decker sandwich, W216-218 dimerization, 12168, 172-176 Isoelectronic series, main group hydride telomerization, 17:168-172 dinuclear complex, 30204-207 polymerization, 12142 reaction, 30:207 reactions with silenes, 39:113-118 structure and bonding, 30205-207 2-Isopropyl-1,3-butadien-3-ylligated allenyl silicon-transition metal complex, cluster, 37:124 W207-208 Isoselenocyanates, properties, 5218-219 reaction, W208 Isostere concept, 9261 structure, 30208 Isothiocyanates, properties, 5211-214 122-valence electron mononuclear Isotope effects, kinetic, Group 14 hydrides, complex 44:103-104 reactivity, 30204 Isotopic perturbation of resonance, 28321 structure, 30:204 128-valence electron mononuclear J complex reactivity, 30203-204 Jahn-Teller distortions, in organometallic structure and bonding, 30201-203 structures, U119 130-valence electron mononuclear Jahn-Teller effect, 1512 complex J modulation test, 28:409-410 reactivity, 30201 Jones-Auer silenes, 39112 structure and bonding, 30200-201 J-resolved two-dimensional NMR spec- Isoflavones, synthesis from chalcones, troscopy 1k190 heteronuclear, 28:432-435 Isomerization homonuclear, 2&426-428 acyl- and alkyl-cobalt carbonyls, 6155 alkenes in hydroformylation, 1213-14 K in nickel-catalyzed oligomerization, Karasch additions, 35247 12123-125 KC(CsH4N)Ph2.3-THF, structure, 43280 carbenecarbonyl complexes, 149-1 1 KCSHs,structure, 43294-295 catalyzed by GIC, 28:107-109 [K(C6H6)l[K(C(SiMe3)2(SiMe2Ph))2],syn- of ketene ligands, 2855 thesis and structure, 43286, 288 olefins, by HCO(CO)~,6:153 K[CSHMe4)2Ti(~'-C=CsiMe~)~l, structure, Isomer shift, in Mossbauer spectroscopy, 43300 935-38 KC9H7.PMDTA,structure, 43304 electric field density at nucleus and, 936 KCsH4SiMe3, synthesis and structure, relation to quadrupole splitting, 974 43299-301 Isonitrile complexes, 85 K2[CsH4( SiPr&-l,5)], synthesis and struc- synthesis and reactivity of, 28236 ture, 43308 Isonitriles K2(CsHs).3-THF, structure, 43318 adducts with lanthanide cyclopentadie- KCgH,.TMEDA, structure, 43304 nyls, 9071 KC13H9.(TMEDA)2, structure, 43305 reactions with KCSMes, structure, 43301 electrophiles, 2263-64 KC(SiMe&, synthesis and structure, silenes, 39131 43283-285 KC(SiMe2Nrne2), 162

KC(SiMe2Nme&, structure, 43289-290 cycloaddition reactions, 2k2, 8-9 KC(SiMe,),(SiMe,Nme,), structure, dimerization, 282 43289-290 free Keilin synthesis, 36:9 addition of nucleophiles to /3 carbon, Kctenc complexes, 22133 2863 hydrogenation, 2854-55 cycloaddition reactions, 2&54 isomerization, 2855 formation on carbonylation of carbene preparation by modification of existing complexes, 28:25-26 complexes, 2829-30 nucleophilic reactions, 2849 pronation with carboxylic acids, 28:52-54 reactivity of, 28:43 spectroscopic characterization, 2832-34 sprectroscopic characterization, structural characterization, 28.34-42 2832-33 synthetic routes, 2830-32 in vinylketene synthesis, 44:330-331 thermal decomposition, 2848-49 HOMO, 282 type I, 2816-17 as intermediates in ethylene hydrofor- nucleophilic reactions, 2849-50 mylation, 26:199, 202-203 structural data, 2834-37 LUMO, 282 type 11, 28:17-18 metal-induced conversion into other or- nucleophilic reactions, 2850 ganics, 2814-16 structural data, 2834, 37-38 organometallic complex reactions addi- type 111, structural data, 2834, 38 tion to metals to form stable com- type IV, 2817-18 plexes, 28:3 structural data, 2834, 39 insertion into metal-ligand bonds, type V, 28:19 283-7 type VIII, nucleophilic reactions, polarization of molecule, 282 2850-51 reactions with coordinated ligands, Ketcnciminc, reaction with disilenes, 39258 287- 11 Ketene ligands transformation bridging, prepared by carbene carbonyla- into carbene ligands, 2811-13 tion, 2824 into other ligands, 2813 complexes with, 28:16-20 Keteniminatometal complexes, by tetracya- coordinated, reactivity of, 2843-55 noethylene insertion into metal-carbon decarbonylation, 2841-49 bonds, 1271 displacemcnt, 28:43-44 Ketenimine complexes, 10158 insertion, 28:44-47 Ketcnyl complexes nucleophilic attack on, 2849-51 reactions of, 2863-66 formation spectroscopic data, 2855-56 by addition of metal carbonyl anions structural characterization, 28:60-63 to chloroacetyl chloride, 2828-29 synthesis of, 2856-59 by deprotonation of metal acyl ligands, .r)'-Ketenyl complexes, 2842 28:26-27 $-Ketenyl complexes in organometallic complexes, synthetic formation of, a31 methods, 2821-32 structure of, 2842 Ketenes synthesis of, 2857-58 addition to unsaturated organometallic p2-T'-Ketenyl complexes, synthesis, 2858 complexes, 28:21-22 p2-.r)' Ketenyl complexes, 2842 arsenic-and phosphorus-substituted, 2831 Ketenyl compounds, formation from transi- coordinated tion metal carbynes, 2275-77 electrophilic attack on, 2851-54 Ketenylidene complexes nucleophilic attack on, 28:49-51 Characterization, 2866-68 163 Lactonecarbonylcobalt complexes

cluster expansion reactions, 2875 Kinetic isotope effects, Group 14 hydrides, reactivity, 2872-75 44:103-104 electrophilic behavior, 2873-74 Kinetics nucleophilic behavior, 2874-75 carbon monoxide, 28182 sprectroscopic characterization, 2868 mercury alkyls, 2102-103 structural characterization, 2870-72 silene reactions, 3914-150 synthetic methods, 28:68-70 dimerization, 39108 Ketenylidene ligands, 2474 formation, 39:90-92 p'-Ketenyl ligand, reactivity, 2863-65 intramolecular reactions, 39140 @*-Ketenylligand, reactivity, 2865-66 Kinetic stabilization, 38204 p-Ketogermanes Kinetic studies chemical properties, 2149-152 arene displacement by phosphines, 1382 rearrangements, 21.50 arene exchange reactions, 1381-82 preparation, 2143, 146 isomerization of carbenecarbonyl com- spectra, 2146-147 plexes, 1410-11 Ketone-metal complexes, 1457-58 olefin oxidation in acetic acid, 13391-394 structure of nickel compounds, 1457 oligomerization of allenes by nickel com- Ketones plexes, 14273 cocyclization with butadiene, 12178 oxidative addition reactions to Vaska's via hydroformylation, 1213 complex, 7:164 insertion into metal alkyl bonds, 285 platinum-catalyzed hydrosilation, 12413- intermediate, in reduction of carbonyl 415,431-432,435-439 compounds, 28102 substitution reactions of metal nitrosyl reactions with carbonyls, 2235 anionic transition metal hydrides, Kish graphite, 2888-89 2241-43 K2[MC4],arylation of, 28224-225 disilenes, 39:255-256 [K(@-~,~s-CSHS)zNd(OCgHjMez-2,6)Z1, doubly bonded germanium com- structure, 43:336 pounds, 39:295-296 KNd(OC6H;Pr2-2,6)4, structure, 43:335-336 silene cycloadducts, 39123-124 Koopman's approximation, 34150 a$-unsaturated, reduction of, 28103-104 Koopman's theorem, 157-9 Ketone synthesis K[PhCHNCHPh].PMDTA, synthesis and from acid halides structure, 43323 and organocopper compounds, [K(TMEDA)(THF),][C24H12]rsynthesis and 12:278-283 structure, 43331-332 and organozinc compounds, 12112 Kurtz powder technique, measurement of from epoxides, 6:144 organometallic second-order nonlinear by 0x0 reaction, 6:135-136 optical properties, 42301-303, 315, p-Ketosilanes 318-319, 321, 324 chemical properties, 2149-152 spectra, 2146-147 synthesis, 2143 L 0-Ketostannanes chemical properties, 7:149-152 P-Lactams, synthesis with monocationic co- spectral properties, 2146-147 balt-alkyne complexes, 4k98 synthesis, 2143, 146 cis-p-Lactams, stereoselective synthesis, Ketyl radicals, from Grignard reagents and a300 ketones, 15:276 Lactonecarbonylcobalt complexes, K[ T~-N(S~M~'~BU)C'BU(CH)~S~M~'~B~],12341-343 synthesis and structure, 43320 hydrogenation, 12,342 Lactonecarbonylcobaltcomplexes 164

Lactonecarhonylcobalt complexes, struc- alkyls, 24:136 ture, 5124 divalent compounds, M158-160 Lactones, synthesis by 0x0 reaction, four-center reactions, M141, 143 4:262-264 homoleptic compounds, 24:136-139 y-Lactones, via selective hydrogenation of acetylides, M138 acid anhydrides, 11326-327 metallation reactions, M138 Ladder compounds ylides, 24.138 polygermanes, 3119 hydrides, a141 polyhedranes with silicon, germanium, acetylides, 24157 and tin, 37:l-36 ionic cyclopentadienyls, a131 polysilane, 3111 low chemistry, 24153-160 Lamellar compounds, 2889 via metal vapor reactions, 24154-158 Lanthanide complexes with carbon monoxide, 24:155 adducts with carbonyls, 23238-241, 251, with cyclooctatetraene, 2155 255 with cyclopentadiene, M155 m-arene, 36:304-306 with nonreducible organics, 24155-157 bis(cyclopentadienyl), 36:322-333 pentamethylcyclopentadienyls, cyclooctatetraene, 36307-309 24160-172 homoleptic alkyl, 36286-289 in low valence states, 24:165-171 homoleptic phenoxide, 36314-315 reactivity vs. metal atomic number, isocyanide, 1k81 2135 via metal atom synthesis, 1588 stabilization, 24:133 monocyclopentadienyl, 36:310-322 synthesis tris(cyclopentadieny1). 36347-350 of lanthanide-carbon bonds, Lanthanide compounds 24:136-144 effects of 4forbitals. 24:132, 134, 154-155 of lanthanide-hydrogen bonds, electron-transfer reactions, 24133, 153 M144-153 oxidation states, 24133, 153 from metals, M153-154 similarity to alkali and alkaline earth ele- zero valent compounds, 24:154-158 ments, 24.133 in catalyzed hydrogenations, M157 Lanthanide organometallics, 24131-177 Lanthanides, 9:362-365 bis(cyclopentadieny1) derivatives, 24:136, s-adducts, 36301-304 139-141 alkoxides, 36289-293 with acetylide bridges, 24150 alkyls, 3245 and alkene polymerization, 24:143 his(cyclopentadieny1s) hydrogenolysis, 24141-143. 148,150 insertion, 36:324, 328-329 metallation, M143, 150 kinetics, 36:329 bis(cyclopentadieny1) hydrides, 24144- ligand variations, 36:333-338 153, 170-172 mechanistic studies, N328 alkene hydrogenation, 24152 precursors, 36:323 dimeric structures, 24A44-145 reactivity, 36:325, 329, 333 via &hydrogen elimination, 24145-148 structural studies, 36:325, 327, 330 via hydrogenolysis of alkyls, carboranes, 36309-310 24:141-144 characterization, 36:284 metallation, 24:150 y-C-H-Ln vs. P-Si-Me-Ln interactions, reactivity, 24:150-152 36341-343 trimeric compounds, M146-150 (CSMe& Ln reactivity and structure, comparison with transition metal com- 36:338-340 plexes, M134-135, 137, 157 decomposition, pathway, 36285 of cyclooctatetraene, 24:155-156 divalent cyclopentadienides, 9:378-380 165 Lewis acids

general chemistry, 9362-365 nitrogen, 3440-443 heterocyclopentadienyls, 36310 organoselenium, 5:83 interactions, 36341-343 organosulfur, 557-58,64, 70,72-73, 80 isocarbonyls ,36340-34 1 organotellurium, 583 ligands, nitrogen donor, 36294-301 redistribution reaction, 6247-250 porphyrins, 36294-299 tetra-alkyls, %245 low-oxidation-states, N344-347 preparation, 2245-247 magnetic properties, 9363-364 reactions, 2247-249 organic derivatives, 9361-380 unsaturated, 2257 organolanthanides, %350 Lead-lead bond selenides, 36293-294 cleavage, 473-77 stabilization, 3Ik285-286 by oxygen, 475 tellurolates, 36293-294 dissociation, 4:72-73 thermodynamics, 36343 length, 471 thiolates, %293 Lead(I1) organic compounds trivalent cyclopentadienides, 9:367-376 v6-arene complexes, 19127-128 Laser, CO, for IR kinetic spectroscopy, bis(bistrimethylsilylmethyl), 19136-137 25291 carboranes, 19135-137 Laser flash photolysis $-cyclopentadienyl chloride, 19125, 128 methylphenyldisilylbenzenes, 3999 dicyclopentadienyl, 19124-125, 127, 1-methyl-1-vinylsilacyclobutanedecompo- 129-131 sition, 3992 dimeric iron carbonyl derivative, silene dimerization, 39108 B145 Laser flash photolysis, radical and iodine, 19129 direct LFP, M71 and Lewis, acids, 19130-131 LFP-clock method, M73 protolytic cleavage, 19131 LFP-probe method, M72 structure, 19:124-125 Leaching, metals by alkyl bromides, and tcne, 19:131 3871-74 and tcnq, 19131 Lead transition metal derivatives, 19143, anionic hydride complexes, spectroscopic 145-147 properties, 224 Lead-sodium alloy, in preparation of tetra- biomethylation, 20329-330, 347 ethyllead, 3868-69 via methylcobalamin, 20319-320 Lead transition metal complex, see Germa- in sediments, 20331 nium, tin, and lead transition metal heterocarborane, 30137-140 complex geometry, 30137-138 Lewis acid-base complexes, 392-3 structure, 30137-138 Lewis acidity, of boron heterocycles, synthesis, M117 18302-303 organic derivatives, 463-77 Lewis acids IT complexes, 26279-281 and bases, adducts with organometallic arene complexes, 26281 pseudohalides, 5196-197 cyclopentadienyl complexes, effect on olefin metathesis, 16312-313 2k279-281 manganesepentacarbonyl alkyl reaction, dicarbollyl complexes, 26281 32184- 185 structures, 26:280 and nickel complexes as oligomerization terphenyl derivatives, M33-39 catalysts, 12109-112, 170 Lead compounds reactions with introduction of functional groups, 2249, anionic transition metal hydrides, 252-256 2230-33 Lewis acids 166

phosphinocarbenes field strength, effects on olefin metathesis Group 13 acids, 44A94, 196-197 catalysis, 17:451 Group 14 acids, M193-194 geometry, of borabenzene metal com- transition metal carbynes, 2281-82 plexes, 25203 rheniumpentacarbonyl alkyl reaction, iron carbonyl complex, k1, 3-4, 10, 24 32207 from ketene transformation, B:13 in synthesis of transition metal carhynes, lahilizing, role of nucleophilecarbonyl ad- 2256-59 ducts, 28~172-175 Lewis bases metal acyl, deprotonation of, 28:26-27 coordination by molybdenum and tung- metal coordinated, reactions with ke- sten alkoxides, 22319, 327-328 tenes, 287-11 metal carbonyl derivatives, 8:4-6 methylene and phenylcarbene, conforma- reaction with phosphinocarbenes, M199 tion, 25163 Lewis basicity, of transition-metal complex order of a-acceptor ability, 3191 fragments, 18303-304 a-bonded hydrocarbon LFP, see Laser flash photolysis acylclic, Group 4B carhonyl complexes Ligand association reactions, computer rcp- containing, 25372-374 resentation, 26179-180, 191 carbonyl complexes not containing, Ligand dissociation reactions 25319-322 computer rcpresentation, 26180, 191 phenylcarbene, trans influence, 25163 in tricarhonyl-T~Z-trienechromium com- representation in TAMREAC, 26:171 plexes, 26330 transfer reactions of borabenzene metal 25:226 Ligand exchange, in substituted q4-diene- complexes, Ligand solvation, in alkali metal organics, metal carbonyls, 26:310-311 22181 -1 85 Ligand exchange reactions anion solvation, 22185 ferrocenes and arenes, 1091 chelating agents, 22185 nickel carhonyl, 210-12 heteroatom effects, 22184 synproportionation, 1093 ion pairing and aggregation, 27:184-185 Ligand properties solvation energies, 22182-184 aryl ligands, U2-3 Ligand substitution reactions, in metal n- phosphinocarhenes complexes, 10347-409 44:209-210 2-electron ligands, acetylene complexes, 10:352-355 U210-213 4-electron ligands, a-ally1 complexes, 10371-378 U1-2 steric crowding, n-arene complexes, 10365-370 terphenyl ligands, &lo-27,29-50,52-58 s-cyclobutadiene derivatives, 10:378-383 Ligand replacement reactions, substituted a-cyclopentadienyl complexes, cobalt carbonyls, 4246-253 10383-409 Ligands mechanisms, 10:389 alkyl, coordinated, 287-8 nature of transition state, 10348 carbene, 2811-13 olefin complexes, 10355-365 carbene, rearrangement, 25155 rearrangement of ligands, 10351 cone angle, and racemization of chiral Ligand substitution reactions, of N-, 0-,S-, complexes. 18175- 176 and Sc-substituted Ru, Os, and Ir car- displacement, iron carbonyls, k28-29 hene complexes, 25154 dynamics Ligand transfer reactions, 4108-111 allenylic hydrocarhyl units, 32100-107 mechanism, 4110-111 allenylidene ligands, 32106-107 Linear free energy approach, 36131-132 electronic character, effect on catalytic Linear polystannanes synthesis, 865-66 properties, 38210-214 167 Lithium coordination complexes

reactivity, 38214-215 physical properties, 27:174 structure, 38208-210 polyhedrane synthesis, 326-8, 29 synthesis, 38205-208 reaction of dialkylcuprates with qp-unsat- [LiOC,H2(2-CH2(2Na)-4,6-Me,l,, synthesis urated carhonyls, 15275 and structure, 43273-275 reactions Lipid solubility of drugs, increase by silyl with acyclic pentadienyl ligands, %127 suhstituents, 18:282 with l-chloro-2-~-(dimethylamino)phe- Literature nyl] tetramethyldisilane, 3836 of organometallic chemistry, B31-35 with chlorodisilane, 3835-36 Main Group elements, 13453-542 with 1-chloro-2-phenyltetramethyldisi- of organotransition metal chemistry, lane, 3835-36 1k447-468,12:379-404 with dichlorodisilane, 38:27 Li(THF)(12-crown-4), 39186, 371 disilane cleavage with, 382-4 Lithiation reactions, use of ultrasound in, with dodecamethylcyclohexasilane, 25104-1 06 38:26, 32, 34-36 l-Lithio-l-f-butyl-2,3,4,5-tetraphenylsilacy- salts clopentadiene, 38:23 Group 1 terphenyl derivatives, 44:6-9 Lithiodiazomethane, 9400, 402, 405, of transition metal hydrides, 276-8, 414-415 19,24-26 1-Lithio-2,6-diethylbenzene, 38221 solvation energy, 22182 Lithiodiorganocuprates synthesis of compounds via metal atoms, preparation, 12:217-220 El05 reactions, with P-bromostyrene, tetrakis(trimethylsilyl)aluminate, 3813 12253-254 Lithium alkyls coupling with organic halides, 12259 exchange reactions, 8168-170 metalation, 12:225 redistribution, 6:202 with perhalobenzenes, 12223-224 shape of HOMO, 20294,296 with vinylic halides, l2269 stepwise addition of butadiene, 6:3 structures, 12.236-237 transmetallation equilibria, 6202 Lithio(diphenylphosphino)ferrocene, Lithiumamido(fluorosilanes), 39194 32155, 282 Lithium-N,N’-bis(2,4,6-tri-t- 5-Lithio-5-methyldibenzosilole, 3825 butylphenyl)pheynlsilaamidide, 39185 l-Lithio-l-methyl-2,3,4,5- Lithium complexes tetraphenylsilacyclopentadiene, 3824 acyclic pentadienyl Lithium, see also Organolithium com- reaction with electrophiles, 26132-133 pounds structure, 26128, 131 aluminum tetraethyl, structure, 3385-386 synthesis, 26:127, -2k128, 26131 base affinities, 27:183 aryl, 288 bonding in alkyls, 15238-239 reaction with nickel carhonyl, 847 bridged electron-deficient compounds, cyclohexadienyl, 16:188 15255-262 phenylethynyl, 38122 diphenylphosphide, 38164 Lithium coordination complexes, X-ray fluoride-iminosilane adducts, 39170- 171, structures 180-183 alkoxides, 24424 heterocyclopentadienide, 39:326 amides and imides, M425-430 naphthalenide, 39:290, 303 binuclear species, 24:425-427 polyhedrane synthesis, 326, 24 hexanuclear species, 24430 organic derivatives, 3365-393 monomeric species, 24425 radical anions, 15275 pentanuclear species, 24:429 phosphanide, 39202, 204 tetranuclear species, 24428-429 Lithium coordination complexes 168

trinuclear species, ?A428 of benzophenone derivative, 2391 carboxylates, 2421-423 benzyl compounds, 22196-198,201 hexacoordination, a423 bond lengths, 22186 tetragonal pyramidal species, X423 bridging, 27:177-178 with tetrahedral geometry, 24.421 with bridging lithium atoms, 24358-366 trigonal bipyramidal species, U422 of acetylene, 24387-388 di(t-butyl) phosphide, M431 acetylide, U363 enolates, 2432-434 allenyl dimers, 24:386-387 five-coordinate compounds, 24415-418 cumulene derivatives, 24:386-390 0-bonded metal derivatives, dilithiodibenzylacetylene, U390-391 U440-441 dimers, 24358-360 tetragonal pyramidal cations, in monomeric structure, 2360-363 24:415-418 from nonadiyne, 2386 halide-bridged metal complexes, tetrameric diyne derivative, 24:388-389 2436-437 coordination, 22176 heptacoordinate cation, U420 cyclopentadienyl derivatives, 22201, 203 hexacoordinate species enolates, 22252-253 cations, 2419 general characteristics, 2354-355 halide-bridged metal derivatives, graphite intercalates, 27:208 24:440-441 ionicity, 22174-176 hydrogen-bridged compounds ligand solvation, 22181-185 of aluminum, 24:438 lithium-carbon bond length and carbon of boron, 24:441 N-bonded four-coordinated species, hybridization, 24363-366 24:413,436 with lithium octahedron, 24:371-372 0-bonded species with lithium-s interactions, 2374-385 four-coordinate monomers, a411-412, allyl, 2374-375 435-436 benzyl, 24377-379,385,391 with lithium bridges, 24414 cyclopentadienyl, 24375-377 three-coordinated metal derivatives, dilithioacenaphthalene, 24:380-381 2438-439 dilithioanthracene, 2378, 381 0,N-bonded metal derivatives, 2437 dilithiobifluorene, 24382 trimethylsilyls, 24.431 dilithiodibenzyl ketone, 24:382, 385, Lithium(fluorosilyl)phosphanide, 39200 391 Lithium(fluorosilyl)phosphanylides, 39:195, dilithiohexadiene, 24:3382, 384 198 dilithionaphthalene, 2378, 380, 390 Lithium-graphite compounds, 28:94-95 dilithiostilbenes, 2382-383 Lithium hydrazines, crystal structures Auorenyl, 24378-379 dilithiated bis(silyl)hydrazines, &14-17 indenyl, 24378,380 monolithiated bis(silyl)hydrazines, 4090- triphenylmethyl, M378 12, 14 with lithium tetrahedra, 24366-370 mono(silyl)hydrazines, &4-6 acetylides, U370 tris(trimethylsilyl)hydrazine, &19-20 alkyls, M366-367 Lithium iodide, manganesepentacarbonyl al- aryls, 24:368-369 kyl reaction, 37:188 cyclopropyl derivative, 24:366-367 Lithium organometallic compounds, X-ray 2,6-dimethoxyphenyl dimer, 24372-373 structural analysis, 22169-277 methoxybutyl derivative, U366-367 aggregation, 22178-181 mixed metal compounds, 22211-212, alkynyls, 22195-196 214-217, 219, 226, 229 aryls and alkenyls, 27:192, 194 mixed metal derivatives, 24392-411 169 Magnesium

allenyl cyclooctadiene cobalt, 24404- Lithium(trimethylsilyl)arylphosphanide, 405, 407 39200 aluminum imino compound, Local oscillating diplole method, 10214 24409-410 Low energy electron diffraction, and study bis(cyclopentadieny1)molybdenum and of heterogeneous catalysts, 12368 tungsten hydrides, 24:403 Lowest unoccupied molecular orbital, 282, bis(norbornene)nickel, 2400 33135-140,3470, 158-159, 164, chromium, M395-397 33139-140 cyclododecatrienenickel, 24400-401 Luminescence, metal-alkynyl complexes, cyclooctadiene cobalt, 24399-400 3888 cyclopentadienyliron, M401-402 LUMO, see Lowest unoccupied molecular dilithioferrocene oligomers, 2402- orbital 403,405 Lutecium complexes dinitrogen nickel, 24:405-409 alkyls, 2136-137 erbium, 24:395-396 bisfcyclopentadienyl) butyl compound, ethylaluminum, 2393-394 2140, 146 ethyleneiron, 2399-402 carbonylation, 24140-141 hydrogenolysis, M142 gold, 24:396-397 bis(cyclopentadieny1) hydrides, 2142, methylberyllium, 24:394 145-148, 164, 170 methylboron, 2394 bis(pentamethylcyclopentadieny1) com- methylindium, 24394 pounds, 2162-165 methylzinc, 24394 in alkene polymerization, 2162 molybdenum, 24397-398,403 P-alkyl elimination, 2163 phenanthrenenickel, 2404, 406 metallation, 24:164-165 phenylmagnesium, 24393,404 tetrakis(aryl)dianion, 24:136, 140 rhenium, 24397-398 silylmercurials, 24410-41 1 tantalum carbyne, X409 M trinickel polyene, 24402 tris(phosphine) ethylenecobalt, Magnesium 24402-403 acyclic pentadienyl complexes, 26:130-132 tungsten, 24:397-398 reactions with terminal Li-C bonding, 2356-358 carbonyl groups, 26132 in dienes, 2357 electrophiles, 26132 in lithiated carborane, 24358 ferrous chloride, 26136 in monomers, 2357-358 alkyl, and aryl metal amide, 3k270-271 in silylmethyl derivatives, 24391-392 borane complexes, 2k65 rr Lithium, complexes, 26217-223 bridged electron-deficient compounds, alkene complexes, 26218 1525s ally1 complexes, 2621 8-220 Group I11 derivatives, 19262-263 in solution, 26220 derivatives of terphenyl ligands, M13-14 cyclopentadienyl complexes, 26221-223 dihalide complexes, 32211-213 bond lengths, 26221 Group 13 elements, complexes with, inverse sandwich structures, 26219, 223 32:214 structures, 26:219 Group 14 elements, complexes with, transition metal, 1997-122 32214 Lithium reagents, in preparation of organo- Group 15 elements, complexes with, copper complexes, l2:217-221 32214 Lithium sila-enolate, 3822 miscellaneous complexes, 32217-222 Magnesium 170

mixed alkali metal compounds, 2R220 Magnetic splitting, in Mossbauer spectros- nitrogen complexes, 32214-217 copy, 9:41 nontetrahedral coordination Magnetic susceptibility di- and tricoordination, 32171-173 determination by NMR. 3:4 penta- and hexacoordination, measurements, n-ollyl complexes, 32173-175 8104-1 05 organic derivatives, see Organomagnes- Magnetization transfer experiments ium compounds with decoupling, 24k446-448 oxygen complexes, 32214-217 measurements in, 28445-446 n complexes with selective pulses, 28448-450 alkene complexes, 26232 Magnetization transfer techniques, in NMR cyclopentadienyi complexes, spectroscopy, 16221-222 26:232-236 Main group elements, n-complexes, diene complexes, 26:233, 236 26:217-295 indenyl complexes, 26:233, 236 Main group organometallic compounds, phenyllithium derivative, 24:393, 404 mass spectra, 6312-315 polyhedrane synthesis, 37:6-8, 26 Main group-transition metal (E-M) clusters rearrangement of organoderivatives, characterization 16:131-165 extended X-ray absorption fine struc- Magnesium-alkyl halide reaction, 3866-67 ture, 42128-129 Magnesium dicyclopentadienide, 2369-370 mass spectrometry, 42127 Magnesium-graphite, 28:125-126 NMR, 42127-128 Magnesium, tetrahedral coordination X-ray diffraction, 42128, 130 cyclic complexes element group, effects on behavior, 423 coordination geomctry, 32169-171 Group 15 element compounds single crystal packing, 32169 structure and bonding factors thermodynamic analysis, 32170 antimony, 42129 dimeric complexes coordination geometry, 425 coordination geometry, 32163-164, edge-bridged tetrahedral molecules, 166 4223,25-26 crystallization conditions, 32160, 165 E-E compounds general structure, 32159 E2 fragments, 4244-52 monomeric complexes E7 fragments, 4252-57, 59 bond angles and bond lengths, E4 fragments, 4259-61,63-64 32160-161 E5 fragments, 4264,66 coordination geometry, 32162-163 E6 fragments, 4267-70 early crystallographic studies, 32160 E, fragments, 4270-73 general structure, 32159-160 Ex+fragments, 4273-76 polymeric complexes Zintl ions, 4243-44 coordination geometry, 32167 electronically unsaturated molecules, crystallization conditions, 32:160, 4212-14,17-19 166-167 ER,(ML,),, type general structure, 32168 electron-precise compound with powder diffraction, 32167 M-M bonding, 4210-12 single crystal techniques, 32167-169 open compounds, 426-10 Magnesocene, see Dieyclopentadienylmag- (p4-E),M, compounds, 4227-28, nesium 30-33 Magnetic properties (ps-E),M, compounds, 4233-35 metal nitrosyl complexes, R233 interstitial E atom compounds, 4235, transition metal alkyls(aryls), 7:173 37-42 171 Manganese carbonyl derivatives

trigonal bipyramidal E2M3mole- decacarbonyl, reaction with liquid ammo- cules, 4220-23 nia, 1821-22 synthesis hexacarbonyl cation derivatives, reaction alkylation, 42100 with amines, 1824-25 Branstead acidbase properties, indium compounds, 3961 4211 6- 11 8 neutron capture and decay, 1k209-210 elimination reactions, 4273-83 pentacarbonylalkyl, stereospecific carbon- halogenation and dehalogenation re- ylation, 18153 actions, 42107-109 pentacarbonyl anion inidene complexes, reactions, 42102 oxidative elimination with iodine cya- ion metathesis, 4276-80 nide, 1812 ligand eliminatiodaddition, in redox condensation reactions, 4297-100 18234-235,240 main group element fragment inser- propadienylidenes, 2283-84, 101, tion into M-M bonds, 42110 110-111 main group oxide reduction via car- reactions, 2286-87 bonyls, 4294-97 silametallacyclopentane, 19216 main group reactions with transition- Manganese, acyclic pentadienyl complexes metal complexes, 42102-103 bonding parameters, X140 metal addition and elimination, molecular structure, 26:137, 142, 155 4288-92 oxapentadienyl complex, 26155-156 metal exchange reactions, 4292-93 pentadienyltricarbonyl complex, 26149- 150 metal insertion into E-H bonds, Manganese carbonyl compounds, anion de- 4283-87 rivatives, 2202-218 organic substrate reactions, acyl derivatives, 2208-210 42121-127 alkyl derivatives, 2:216-217 oxidationireduction processes, ally1 Mn pentacarbonyl derivatives, 42118-121 2213-214 polyphosphine/polyarsine reactions, n-ally1 Mn tetracarbonyl derivatives, 42103, 107 2213-214 redistribution reactions, 42102 heavy metal derivatives, 2204 substitution reactions, 42114-116 hydrides, 2205 synthesis, Zintl ions in, 4287-88 mercury derivatives, 2215 thermolysis/photolysis reactions, Mn-H bond, 2212-213 42110-114 nitrosyl derivatives, 2217 nomenclature, 424-5 other anionic derivatives, 2217-218 stability, 422, 130 periluoroalkyl derivatives, 2209, 212 Maleic acid, catalyzed hydrogenation to suc- sodium salts, 2203 cinic acid, 16263-264 tertiary substituted phosphine derivatives, (R)-Mandelic acid, in spirocyclic A%-sili- 2:206-207 cates, ligands, 44941 transition metal derivatives, 2215 Manganacycles, 37:199-200 triphenyltin derivatives, 2214-215 Manganese Manganese carbonyl derivatives, 3213-223 carbonyl halides, reactions, 3217-221 as hydrogenation catalysts, 17:336 halogenation, 3216 mass spectrum, 6278 nitrosyl complexes, 3215-216 carbonyl nitrosyl, 822 perfluoropenyl compound, 347 cyanocarbonyl anions, 1837 substitution, 3219-220 binuclear, 18:40 trimethylene compound, 326 Manganese 172

Manganese, carbyne complexes CO dissocation rate parameters, 2k117 bonding, 2252-53 of pentacarbonylbromide, 2k137-138 reactions of pentacarbonyl radical, 2k143-144 carbyne coupling, 2284 chiral Schiff base, 18163,196 with nucleophiles, 27:70-71, 74,77 decacarbonyl, see Decacarbonyldiman- structure, 2255 ganese synthesis, 2258,66 decarbonylation of acyl derivatives, Manganese, chiral cyclopentadienyl nitrosyl 1k107 phosphine complexes I ,4-diaza-l,3-butadienes circular dichroism, 18170-171 binuclear hexacarbonyl, 2k162-163 ligand transformations, 18:169-171 with chelated ligand, 2k160-161, of optically active aminophosphines, 176-178 18160-161. 176, 187 ligand activation, 21:228-229 optical resolution, 18:154-155, 160-161 mixed cobalt compound, 21:162-163, racemization of aroyls, 18172-176 177,195,205,208-209 Manganese complexes with douhle bond to germanium, alkyl, 38108,110 2k274-216 alkynyl. 38108,110, 114-115 formyls, 206-10,16 anionic hydride decomposition, 2026-27 reactions with Lewis acids, 2232-33 p-germylenes spectroscopic properties, 275,23 MO calculations, 20234-235 structure, 229 structural data, 20233 arene, 1365,78, 90-91 heptacarbonyl diene, 26362 assisted carbonyl insertion reactions hetcrocarborane bonding, 30:143-144 by alumina, 23284-285 hexacarbonyldienediyl, 26355-356 by amphoteric molecules, 23287 with isocyanides, 1k54-57 by Lewis acids, 23282-283 electrochemical studies, 1k27 by protons, 23281 nucleophilic reactions, 1k37-38 bimetallic, 32229-232,234, 240, 244-246, isodiazene, 23186-188 251-253,276-277, 283-284,288-280, isoelectronic, 30204-207 291,293-295,297, 305-306, 308 main group binuclear n-C.0-bonded carbonyls, bismuth, 3k137-139 23268-270 gallium, indium, and thallium, boranes, 21:63-66, 68-69,85-88, 95 3k96-101 "B NMR spectra, 2k82 germanium, tin, and lead, 3k113-117 tetracarbonyl of oclahydrodiborate. tellurium, 31:157-165, 172 2k88-9 1 mass spectra, 8234-239 tricarbonyl of octahydrotriborane. cymantrene derivatives, 8235-238 21:89-90, 105 via metal atom synthesis, 1594 broadening of "C NMR spectra. 12138 p-methylcnecarbonylcyclopentadienyls, carbamoyl, 1fk30-31 20164-165 carbonylation, 11:122-125 mass spectra, 20215 carbonyl-bridged ytterbium derivative, MO calculations, 20198-200 24166 NMR spectra, 20214-215 carbonyl diazene. 3498 oxidation, 20200-201 carbonyl halides, rcactions with isocya- photoelectron spectra, 20197-198,246 nides. 1k.55 X-ray structure. 20165, 190, 208 carbonyl substitution mechanisms nitrosyls association and nitrosyl ligand, carbonyl anions, 2447 21: 123 - 124 clusters, 2447,50. 52-54,57-59 173 Manganese vinylidenes

octacarbonyl diene, 26353-354, 358, 362 isocyanides, 2310, 22-23 octafluorocycloocta-l,3,5,7-tetraene, isomerization, 2320-21, 23 31:205-211 nitrosyls, 23:24 2-oxocyclopentylidene, 20185 phosphine halides, 2319-21 7i-cyclopentadienyltricarbonyl,organic de- phosphines, 2323 rivatives, 1047-50 cyclopentadienyls, 2369 pentacarbonyl diene, 26356-357,359 carbonyls, 23:49-52 pentacarbonyl( cr-cyclopentadienyls), catalytic oxidative substitution, 2k21-23 2351-52 phenylethynyl, 38123, 136 dinitrogen derivatives, 2351 photochemistry nitrosyls, 2352 binuclear carbonyl cyclopentadienylvi- decacarbonyl derivatives, 24.102, 122 nylidenes, 24:337-338 ligand-bridged bimetallics, 24100 dicarbonyl cyclopentadienyl alkyli- Manganese isocyanides denes, 24335-337 carbonyls, 22230 pentacarbonylalkyls, 24288-291 binuclear, 22215, 244 pentacarbonylphenyl, U291 fluxionality, 22239 radiochemical studies, 11:217, 240-241, redox reactions, 22255 244 cyclopentadienyls, 22216-217, 225 (C5H5)Mn(CO)3, 11:217,230-231 homoleptic species, 22222, 233, 243 Mnz(CO)lo, 1k229 Manganesepentacarbonyl alkyls, 32170-171 RMn(CO)5, 1k232-233 reactions, 32183-206,213 reactions with bis(trimethylsilyl)diazene, with cationic species, 37:187-188 23184-1 86 with Lewis acids, 32184-185 redistribution of alkyl carbonyls, 23:120 with silyl ligands, 11:255 with nucleophiles, 32188-206 sulfur dioxide insertion reactions, l2:62 orthometallation, 32185-187 terminal 2-C,O-bonded carbonyls with transition metal hydrides, with alkali metals, 23228-230 32183-184 with aluminum compounds, 23238 structure, 32177-183 of dppm, 23220 diffraction studies, 32177-178 with lanthanides, 23:238, 240-241 spectroscopy, 32178-182 with magnesium ions, 23235-236 synthesis, 32171-175 tetracarbonyl(3.) anion, see Tetracarbon- Manganese, $-SiH complexes ylmetallate(3-) anion of manganese bond length, 30:16.5-167 and rhenium "C NMR spectra, 30161-162 tetracarbonyldiene, 26:353-358, 362 infrared absorption, 30:157 synthesis, 26:355 isoelectronic, 30207-208 thermal carbonyl elimination, 26357 kinetic investigation, 3015.5, 168 tetraphenylarsole, 13:255-256 molecular orbital interaction, 30163 tncarbonyl cyclopentadienyls, 2k21-24 neutron diffraction analysis, 30:158-160 polycyanovinyl, 2k44 preparation, 30154-155 trimetallic, 32276-277, 298 related complex, 3O:170-174 p-vinylidene, 20189 "Si NMR data, 30166-167 Manganese complexes, electron-transfer re- Manganese vinylidenes actions binuclear cyclopentadienyls, 2269, 76, binuclear cyclopentadienyls, 24102-103 102, 108, 112 butadiene, 2338 nucleophilic attack, 2282 carbonyls, 2318-24, 78 protonation, 2281 halides, 2320 reaction with metal complexes, 2276 Manganese vinylidenes 174

cyclopentadienyls, 22:63-64, 66, 69, 89, appearance potentials, 6315-323 100, 104-105, 122-124 a-arene complexes, 6285, 293, 302 bonding, 2297-98 carbonyl halides, 6283, 298-299 phosphine substitution, 2272, 74 carbonyls, 6275, 298 reaction with alcohols, 22:70-71 a-cyclobutadiene complexes, 6285, 301 thermolysis, 22114 s-cyclopentadiene complexes, 6285, Manganocene 299-300 magnetic properties of substituted com- ferrocenes, 6304, 308 pounds, 40.155-156 fluorocarbon derivatives, 6292,302 polymeric structure, 40:154-155 heats of formation of ions, 6316-323 spin-state crossover and orbital occu- metallocenes, 6:304 pancy, 40.154 with metal-metal bonds, 6:280, 298-299 Mark1 route, 39327 nitrogen ligands, 6294 Masked disilenes, anionic polymerization, nitrosyls, 6282, 298 3838-39 olefin complexes, 6291, 301-302 Mass spectra phosphine complexes, 6294, 302-303 alkyl diboranes, 3289 sulfur ligands, 6294, 302-303 arenemetal complexes, 1354-55 Mass spectrometry cyclosilanes, 7:34 determination of B-B bond energies, dialkylberylliums, h199 10248 diboranes, 3289 main group-transition metal clusters, Group 4B metallocene dicarbonyls, 42127 25351 manganese- and rheniumpentacarbonyl al- hydroplatinum phosphine complexes, kyls, 37:181-182 13354 metal nitrosyl complexes, 7:234 and mixed-metal clusters, 18242-244 organolithium compounds, 3371-372 chemical ionization, 18244 organometallic heterocycles, 13245-251 and redistribution reactions, 23102-103 transition metal alkyls(aryls), R172 silicon-transition metal compounds, Mass spectra, hydrocarbon-metal com- U287 plexes, 8211-327 substituted ferrocenes, 1095-97 benchrotrenes, 8227-231 Mass spectroscopy chromium, molybdenum, and tungsten, copper( 11) benzoates, 12:303 8218-234 silylenium ion cobalt, 8272-276 Fourier transform, halide reaction, cymantrenes, tk235-238 30249 ferrocencs, 8:241-259 ion cyclotron resonance iron, 8:259-271 generation, 30246-247 manganese, 8234-239 reaction kinetics, 30249-250 nickel, 8278-283 tandem rhodium and iridium, 8276-278 generation, 30247-248 ruthenium and osmium, 8271-272 halide reaction, 30:249 technetium and rhenium, 8239-241 Matrix isolation titanium, zirconium, and hafnium, ethylenegold compounds, 2051 8213-215 metal carbonyls, studies, 1564 vanadium, 8216-218 palladium (0) carbonyls, 13368 Mass spectra, transition metal complexes. in transition-metal fragment characteriza- 6273-323 tion, 25278-280 acetylene derivatives, 6291, 301-302 [M( $)-C,H,)(+C,H,-(E)-CH= CHC6H,.4- a-ally1 complexes, 6284, 300-301 N02], nonlinear optics, 42325, 328 175 Mechanism

[MCI2[q’-S=C(C6H4R-p)2)2], synthesis, allylic intermediates, 12143 43143 olefin metathesis, 16285-299, 12449 MC12 halides, arylation of, 28226-227 organolithium-initiated polymerization MC12(tht)2,arylation of, 2&223-224 of dienes, 1865-78 [M(CO),(C(OMe)-(E)-CH=CHNMe2], of olefins, 1861-65 nonlinear optics, 42330 0x0 reaction, 6128 M(C0)4(GeMe3)2,synthesis, 42254 palladium-catalyzed reactions [M6(CO)ISN],structure and bonding fac- butadiene-silane telomerization, 17:164 tors, 4237 C02 with butadiene, 12179 M4(C0)12N2RZ.structure and bonding fac- reductive dimerization of isoprene, tors, 4247 17:172-173 [M(C0)4(1,10-phen)],nonlinear optics, Pt(I1)-catalyzed H-D exchange in al- 42~330-331 kanes, 15169-172 M4(C0),3(PPh), synthesis, 4283 racemization of chiral manganese com- [M(CO)5(Se=C(C6H4R=p)H)] plexes, 18172-174 q’l$isomerization, 43131-133, 177-178 of reduction IR spectroscopy, 43135 coordinated CO by boranes, 1270 NMR, 43:135 organotin hydrides, k66, 69-70,75-80, thermochromic behavior, 43136 82,84 MCPh3.L, synthesis and structure, 43277, zirconium carbonyls, 17:71-73 280 of thermal rearrangement MC(SiMe,Ph),, structure, 43289-290 ally1 silylmethyl ethers, 1650-52 M(C6X,),L complexes, 28254-256 benzyl silylmethyl ethers, 1654-55 [MeC(CH2PPh,)3Co(P,R)]+,synthesis, silyl silylmethyl ethers, 1641-45 42100 Mechanism, metal carbonyl substitution Mechanism, see also Reaction mechanisms by association, 2k122-125 carbamoyl ligand formation, 1825-26 effect of Lewis acid, 2k125 catalytic hydroformylation reaction, electron localization on ligands, 6122-124 2k123-125 catalyzed carbonylation of methanol, carbonyl dissociation rates, 21:116-117 12255-267 metal dependence, 2k116 catalyzed hydrogenation clusters, 2k145 by rhodium complexes, 12321-323 by dissociation, 2k114-122 by ruthenium complexes, 12323-324 activation parameters, 2k116-117, 121 catalyzed hydrosilation, 17:409 n-bonding effects, 21:122 via cobalt carbonyl, 12416-417, 429 ground-state bond weakening, 21:122 ethylene-butadiene codimerization, ligand competition, 2k115-116 12272-275 ligand dissociation rates, 2k116-118 by nickel catalysts, 12291-294 rate constant expression, 2k115-116 by rhodium catalysts, 12272-275 and eighteen-electron rule, 2k122-123 Fischer-Tropsch reaction, 1286-96 by interchange-electron rule, 2k122-131 via carbonyl insertion, 1287-88 activation enthalpies, 2M28 via hydroxy carbene condensation, amine substitution, 2k128-131 1286-87 rate constant expression, 2k126-129 hydroformylation reaction, 6122-124, and isotopic labeling, 2k131-143 123-10, 54-55 IR spectra, 21:132 mercuration, 4:307-308 I3C NMR spectra, 2k132 via metal carbides, 1286-87 matrix isolation studies, 2k141 nickel-catalyzed butadiene cyclization, radical complexes, 2k143-144 12143 site preference, 2k137 Medium-performance liquid chromatography 176

Medium-performance liquid chromatogra- with chelated ligands, 2k167, 193 phy, metal-free cagc compound separa- of molybdenum carbonyl, 2k229 tion. 41:61 germyls, 2k273 Meenvein reaction, 12305 mixed alkali metal, 22247, 252 Mehrkegel molecules, k255 redistribution, 6256-260 Meisenheimer complexes, l2289-290 u-pentachlorocyclopentadienyls,21:26 Meisenheimer salts, of carbanions, 27:243 Mercury divinyl, 335 , substituent effects in metallo- Mercury(I1) chloride, addition to transition cenes, 40.127-128 metal alkyls, 2184 Membranes, use in conjunction with hydro- Mercury silyllithium structures, 24:410-411 genation catalysts, 12367-368 MeSiH3, dehydrocoupling for polymeriza- MeNC4(OSiMe7)2(PPh2)2(PPh?)ZNiPZPhL, tion, 42384 synthesis, 4282 Me2Si(H)NHNHSi(H)Me2, 42396 [M~?PAu)~N]+,synthesis, 4282 Me3SiSiHMez dehydrocoupling for polymer- Mercuration, mechanism, 4:307-308 ization, 42:382 Mercurials, in synthesis of alkylidynetrico- Mesityl azide, 39:216 balt nonacarbonyls, 14103, 105 Mesitylene, in metallic r complcxes Mcrcury gallium, 26245, 247-248 aryls, insertion of sulfur dioxide, a37, indium, 26249, 252 50 thallium, %:257 biomcthylation, 20325-326, 348 Mesitylene ruthenium cyclopentadienyl by humic acid, 20330 complexes, 29186 by microflora, 20325-326 Mesityl isocyanide, 39217-218, 225-226 by sediments, 20331, 348 Mesityl ketones, conjugate addition of Grig- in soils, 20330-331 nard, k228-230 carbonylcobalt complexes, e355-357 Metal acyl ligands, deprotonation of, reactions with alkynes, 12:356-357 2826-27 "C chemical shifts of neopentyls, l2177, Metal alkoxides, multiple bonding, 191 3939-44 u-cyclopentadienyl, 2052 Metal-alkyl bonds, ketene insertion, 28:4-5 divalent salts, reaction with methylcobala- Metal-alkyl compounds, M-C bond dis- min, 20316-318,337 tances, 38105-112 halides, reaction with organocopper com- Metal-alkyl halide complexes, 3862 pounds, 12287 Metal alkyls organic dcrivatives, see Organomercury in aqueous solution, 38155-156 compounds alkylchromium(II1) complexes, in triosmium clusters, 26:76 38156-160 Mercury alkyls alkylcobalt(II1) complexes, 38160-162 electron impact studies, 2104 alkyplatinum( 111) complexes, kinetics of pyrolysis, 2102-105 38162- 163 mean bond dissociation energies, metal-carbonyl complexes, 38163-164 2: 100- 102 bond dissociation energies, 2100-107 radiochemistry, 11:222 M-C bond distances, 38:79, 139-140 silyls, in synthesis of transition metal com Metal alkynes plexcs, 11:265 cleavage reactions, 2990-92 Mercury-carbon bond cleavage, 4304-307 orbital interactions, 292 Mercury compounds Metal-alkynyl complexes, 3879, 139-140 borane, 2k65 bonding, 38:80-82 coupling reaction, 2k104 electronic spectroscopy, 3tk84-88 1,4-diaza-1,3-butadienes molecular-orbital calculations, 3883-84 177 Metal-carbon bonds

Mossbauer spectroscopy, W89 haloalkenes, 1562-63 NMR spectroscopy, 3881, 89 isocyanides, 1566 photoelectron spectroscopy, 3883-84 nitric oxide, 1564-65 vibrational spectroscopy, 38120-139 norbornene, 1561-62 X-ray crystallography, 3890-120 phosphines, 1565 luminescence, 3888 thiophenes, 1584 terminal complexes, 3890-99, 103 trifluorophosphine, 156.5 Metal-alkynyl redox congeners, M-C bond Metal atoms, in synthesis of organometallic distances, 38115-116 compounds, 1553-107 Metal allenyl complexes, see Allenyl com- aluminum, 15106 plexes chromium, 1590-92 Metal allenylidene complexes, see Allenyli- cobalt, 1397-98 dene complexes comparison with other synthetic meth- Metal amide derivatives, multiple bonding, ods, 1586-87 3918-26 copper, 15104 Metal arsenide derivatives, multiple bond- experimental methods, 1555-59 ing, 39:26-38 gallium, 15106 Metal aryloxides, multiple bonding, germanium, 15107 3939-44 gold, El04 Metal atoms Group IIIB elements, WS8 insertion reactions, 1578-84 indium, 15106 with carbon-halogen bonds, 1578 iridium, 1598 main group elements, 1579-80 iron, 1595-96 transition elements, 1580-83 lanthanides, 1588 oxidation reactions, 1583-84 lead, 15107 with acetylacetone, 1583 lithium, 15105 polymerization, 1555 magnesium, 15105 preparation manganese, 1574 in excited states, 1555-56 molybdenum, 1592-93 via metal evaporation, 1555 nickel, 1599, 101 thermally, 1554 niobium, 1589 Metal atoms, reactions palladium, 15100-103 alkenes, 1559-63 platinum, 15100, 103 alkynes, 1563 product yields, 1584-87 arenes, 1572-76 rhodium, 1598 1,3-butadiene, 1568-70 silicon, 15106-107 carbon dioxide, 1564 silver, 15104 carbon disulfide, 1564 tin, 15107 , 1564 titanium, 1589 carbon monoxide, 1563 tungsten, 1593 cycloheptatriene, 1576-77 uranium, 1588 cyclooctadienes, 1566-68 vanadium, 1589 cyclooctatetraene, 1577-78 zinc, 15106 cyclopentadiene, 1570-71 Metal carbenes, and olefin metathesis, deuteropropenes, 1560-61 16299-303, 305-308 dialkenes, 1566-72 Metal-carbon bonds, 38105-116, 136-137 dinitrogen, 1564 of acyl complexes, base-initiated hydroly- ethers, 1584 sis and alcoholysis of, 28185 ethylene, 1559 dihalo and monohalocarbene complexes fulvenes, 1578 of Os, Ir, and Ru, 25173 Metal-carbon bonds 178

dissociation energies, 2100-107 photochemistry of, 32263-265 mean dissociation energies, 298-100 reduction reactions, 32259-263 homolytic cleavage, 38158 unsaturated organic substrates, Metal-carbon g bonds 32304-317 carbonyl insertion, 11:88-139 Metal carbonyl anions, 2:158-160, 2161 radiochemical studies, 1k221-222 addition to chloroacetyl chloride to form Metal-carbon monoxide bond strength, ketene ligands, 2828-29 2~176-178 binuclear species Metal-carbon monoxide complexes, 38114 halide bridged, 1813-14 Metal-carbon triple bonds heteronuclear, 189, 14-15 alkylidyne metal complexes homonuclear, 18:6-12, 15, 18 bonding description, 32242-243 hydrides, 185-6, 8-9, 14 gas-phase studies, 32229, 242 insertion reactions, 1815 matrix isolation studies, 32229, 242 cyanides, 18:12, 36-41 sprectroscopic properties, 32228, of Group VIB metals, 184-19 230-242 halides, 1812-14, 16 structural data, 32:229 inert gas configuration, 2:169-171 structural studies, 32228 reaction with metal halides, 18236-237 surface studies, 32229, 242 Metal carbonyl cations, see Cationic metal background, 32227-228 carbonyls bond dissociation energies, 32242 Metal carbonyl cluster complexes, 1940-45 synthesis of theoretical studies, 1540-45 acetylide ligand reactions. 32249-254 role of bridging groups, 1944-45 acyl ligands Metal carbonyl complexes, 1316-18 oxide abstraction from, 32245-246 in aqueous solution, 38163-164 oxygen abstraction from, 32246-247 bonding, 1317 alkoxycarbene ligands, alkoxide abstrac- as catalysts, 1318 tion from, 32243-244 chalcogen-bridged, see Chalcogen-bridged alkyne ligand reactions, 32253 metal carbonyl complexes a-carbon atoms, removal of substitu- Metal carbonyl cyanides, 818-19, ents from, 32243-249 10168-173 carbonyl ligand rcactions, 32256 Metal carbonyl derivatives, structures, a-hydrogen abstraction, 32248-249 9128-131 a-hydrogen elimination, 32247-248 Metal carbonyl halides, 813-15 isocyanide ligand reactions, 32254-256 mass spectra, 6283, 298-299 metathesis reactions, 32256-259 Metal carbonyl hydrides, 86-9 thiocarbonyl ligand reactions, 32256 reaction with unsaturated fluorocarbons, unsaturated ligands, P-addition, k181-183 32249-256 Metal carbonyl nitrosyls, 821-22 vinylidene ligand reactions, 32249-254 Metal carbonyls vinyl ligand reactions, 32251-253 alkene reaction with, 3277 transition metal alkylidyne complexes bond enthalpies, 2641 coupling reactions, 32293-304 bridged, 820-21 electrophiles, reactions with, cationic, see Cationic metal carbonyls 32277-288 chalcogen derivatives, 819-20 ligand substitution reactions, chemistry in liquid ammonia, 181-53 32265-276 alkali metal reduction, 184-7, 9 nucleophiles, reactions with, borohydride reduction, 186 32:288-293 reaction with bipyridine ligands, oxidation reactions, 32259-263 1842-46 179 Metal complexes

reaction with solvent, 1819-33 and metal-metal bonding, 22173 discovery, 81-24 redox potentials, 22172 early theories, 8:2-3 expansion reactions, 22186-193 high-pressure synthesis, 183, 46-47 auration, 22189 intensities of v(C0) bands in, 10199-233 with carbonyl anions, 22188-191 bond angles from, 10216 with neutral metal compounds, IR spectra, 3187 22192-193 Lewis base-complexes, 3181-252 via oxidative addition, 22:187 ligand substitution mechanisms, framework rearrangements, 22197-200 2k113-150 fluxionality, 22198-199 mass spectra, 6278-280,298-299 metal exchange reactions, 22195-197 redistrubution reactions, 6260 via equilibration, 22196-197 mean and intrinsic bond energies, via expansion and degradation, 2109-1 10 22195-196 neutron irradiation, 1k225-229 via redox process, 22197 Group VI derivatives, 1k225-228 propadienylidene, 22121-122 iron and ruthenium, 1k229 reactions with acetylenes, 22185 nitrogen-donor complexes, 10115-186 reactions with polyfunctional ligands, nucleophile adducts of, see Nucleo- 22180-186 philecarbonyl adducts and cluster unfolding, 22184-186 physical properties, 8:22-23 hydrogenation, 22:180 protonation, 8124 oxidative addition, 22180-181 pyrolysis and cluster formation, triangular face-capping , 22:181- 183 18228-230 two-center addition, 22180-181 reactions, 84-6 reactions with unidentate ligands, with olefins, 1:181, 183-184 22173-179 with perfluoroalkyl iodides, 1:180-181 acid-base reactions, 22174-175 redox condensation with carbonyl anions, addition to double bonds, 22175-176 18233-236 and cluster nuclearity, 22178-179 synthesis metal-metal bond cleavage, 22177-179 in solution, 817-18 protonation, 22:174-175 without solvents, 815-17 size reduction, 22193-195 synthesis of Mo(C0)6, W(CO)6, 1035 by donor ligands, 22193 water-gas shift catalysis, in acidic or neu- by hard bases, 22195 tral solutions, 28191, 196-197 by oxidation, 22194 Metal carbonyl species pyrolysis, 22195 dinuclear, detection by IR kinetic spec- vinylidenes, 22115-122 troscopy, 25307-311 Metal complexes [CpFe(CO)&, 25309-311 C,,W(RC=CR)3(CO), 295 Mn2(CO),", 25308 Cp2M2(CO),, bond order formalisms in, intermediates, detection by IR kinetic 29102 spectroscopy, 25312 Cp2M2(CO),, related systems, 29117-118 Metal carbyne complexes, see Alkylidyne synthesis and spectroscopic properties, metal complexes 29118-121 Metal carbynes, as intermediates in alkyne dicarbonyls, 29120-121 metathesis, 16297 pentacarbonyls, 29118 Metal clusters, 22169-208 tetracarbonyls, 29118-119 carbidocarbonyls, 221-58 tricarbonyls, 29119-120 as electron reservoirs, 22200-201 CpM(RCz CR)X, structure, 2930-32 electron-transfer reactions, 22171-173 C~M(RCECR)~X,synthesis of, 2916-18 Metal complexes 180

cyano, 3881,112-114 fragmentation, 26187-188 cyclopentadienyl, with oxygen atoms, synthesis, computer representation, 28356-369 26178, 187 dioxygen, reaction with ketenes, 28:6-7 nickel, 26:97 M( CO)(RCE CR)2,293-6 niobium, 26:100-101 M(CO)(RC=CR)L2X2, structure, 2924, platinum, 2697 26-28 in reaction of rhodium complex with bi- M(CO)(RC=CR)L,X,, 292-3 cyclobutane, 12466 M(L)(RC-CR)(B-B)*, structure, reductive decoupling reactions, computcr 2928-30 representation, 26179 ML( RC- CR)(B -B)>, 29:7-9 rhenium, 26:100-101 M(RC=CR),L2X2, synthesis of, 2914 tantalum, 26100-101 M(RCZR),(CO), 295 thermolysis, 2697 unsaturated hydrocarbons, 1319-20 titanium, ZkY7 Metal halides, addition to metal complcxcs, tungsten, 26:97-124 273-75 zirconium, 1943-44 Mctal-hydride bonds, ketene insertion into, Metallacyclobutadiene complexes, see Al- m3-4 koxides, molybdenum and tungsten, Metal hydrides metallacyclobutadiene complexes addition to triosmium clusters, 2671-72 Metallacyclobutadienes, 2697-124 complex, reductions with, 3267 in alkyne metathesis reactions, 2698 conversion to carbonyls by protonation, Metallacyclobutanes 8125 via hydride attack of q’-allyls, 12456 Metalla /3 diketonate, 2547-48 in olefin metathesis interligand C-C coupling reactions, conformational and configurational sta- 2560-70 bility, 12474 Metalla /3 diketonato complexes, 25:49-55 decomposition, 12464 Metalla fi diketones, 2548-49 formation of cyclopropanes, 12450 Metalla fi ketoimines, 2556-60 via rearrangement of complexed car- Metallabutadiyne complexes. 38:87. bene and olefin, 12452 109-110 ring puckering and stereoselectivity, Metallacarboranes. 26240. 246 17:473-478 Metallacycles, 2697- 124 of tantalum, decomposition to propyl- and carbon-carbon bond formation, ene derivatives, 17:462, 465 12198-204 thermolysis of platinum complex, via hydride transfer, 12198 17:464 via ligand insertion, 12198 Me tallacy clodisiloxanes in natural product synthcsis, 17:204 in catalyzed disiloxane redistribution, in reductive elimination, 12198 19236-237 via reductive elimination, 12198 of platinum, 19244-245 in carbonylation reactions, 17:225 Metallacyclopentane, as reaction interrne- cleavage reactions, computer represcnta- diate tion, 26:178 in ethylene dimerization, 26198 dicyclopentadienyltitanium, 193, 9, 37, 43 in inetallacycle fragmentation reactions, five-membered 26:186 fragmcntation, computer representa- 2,3,4-Mctallacyclopentatrienes, synthesis tion. 26185-186 and structure, 42200-201 synthesis, computer representation, l-Metalla-1,3-hexadien-5-pes, synthesis via 26184- 185 (1-alkynyl)carbenes, 4k170-171 four-membered 1-Metalla-1,3,5-hexatrienes 181 Metallocarboranes

cyclization reactions, 4k173-177 Metallocarborane complexes, bonding theo- synthesis, 4k171-175 ries, analogy with carbonyl clusters, Metallation 1540-45 alkynes by copper acetylides, a229 Metallocarboranes, 14145-186, 2k60-61 arenechromium complexes, 1367,85 with eleven vertices, 14171-175 carborane, 3320-322 bimetallic species, 14173-175 cyclooctatetraene, 3k245-247 monometallic species, 14:171-173 dienes, 26127 polyhedral rearrangement, 14175 indenofluorene, 26223 reactions, 14173-175 by organometallic compounds, 215-19 structures, 14:171, 174 Metallation reactions, unsaturated fluoro- synthesis, 14171-175 , 3k200 with fourteen vertices, 14171 Metallatrienes, cross-conjugated geometry and number of polyhedral verti- pyranylidene complex synthesis, 4k178 ces, 14148-149 synthesis, 4k177-179 in homogeneous catalysis, 14182-183 l-Metalla-1,3,5-trienes, synthesis, alkene isomerization, 14183 4k219-220 deuterium exchange, 14183 Metal ligand bonds with nine vertices, 14178-180 borabenzene metal complexes, 25204 bimetallic species, 14:180 ketene insertion into, 283-7 NMR spectra, 14179 Metal ligands, coordinated, reactions with structures, 14178-179 ketenes, 287-11 synthesis, 14178-180 P-Metalloalkyl radical, fragmentation, com- oxidative addition to B-H bonds, puter representation, %197 14180-182 Metalloallyl clusters, 3272 in deuteration, 14181-182 Metallobis(methylene)phosphorane, synthe- by iridium complexes, 14181-182 sis with phosphaalkenes, 4k19-20 relative reactivity of BH groups, 14:182 Metalloborane clusters, 21:92, see also Tran- stabilization of high oxidation states, sition metal clusters, boron atoms in 14156 bond distances, 3340-47 synthesis, 14150-155 interstitial compounds, 2k101-102 from nido-carborane anions, NMR data, 3337-40 14150-151 Metalloboranes, 2k57-112 via polyhedral contraction, 14152-153 and alkynes, 2k104 via polyhedral expansion, 14151-152 with bridging hydrogens, 2k84-92 via polyhedral subrogation, 14153 cage coupling, 21:104 by thermal metal-transfer, 14153-154 as chemical intermediates, 21:104-105 with ten vertices, 14175-178 classification, 2k61-67 bimetallic species, 14:177-178 isomerism, 2k94-96 mixed sandwich complexes, 14175 and Lewis bases, 2k104 polyhedral rearrangements, 14175-176 with more than one metal, 2k96-101 reactions, 14178 "B NMR spectra, 2k82-84 synthesis, 14:175-178 polyhedral skeletal electron pair theory, trimetallic species, 14178 2k92-94 thermal rearrangement, 16:341-342 relationship to a-complexes, 2k61 with thirteen vertices, 14167-171 synthesis, 21:67-71 polyhedral contraction, 14:169 from bulk metal, 2k69-70 polyhedral expansion, 14169 by ligand substitution, 2k67-68 polyhedral subrogation, 14:168-169 via metal carbonyl activation, 21:68-69 rearrangement reactions, 14167-1 68 via metal hydrides or alkyls, 2k69 synthesis, 14167-171 Metallocarboranes 182

with twelve vertices, 14155-167 structural energetics, &144-146 bimetallic species, 14166-167 types, 40.118, 138 mixed ligand complexes, 14163-166 mass spectra, 8211-327 monometallic species, 14155-163 benchrotrenes, 8227-231 polyhedral rearrangement, 14158-159 cymantrenes, 8235-238 reactions, 14159-161 ferrocenes, 8241-259 structures, 14157 Mossbauer spectroscopy, substituent ef- synthesis, 14155-159, 161-167 fects Metallocene oxocarbene complexes, 37:270 iron-57 spectra of ferrocenes, Metallocenes, 10322, see also Ferrocene &157-160 definition, 40119-120 tin-119 spectra of stannocenes, electrochemical behavior of substituted &160-161 compounds preparation from thallium cyclopentadie- alkyl substituents, 40:150 nide, 11:152 assay, 40:149 reductive cyclopentadienide elimination, gas-phase ionization energy correla- 19:111-120 tion, 40.151-152 substituent effects on synthesis and sta- solvent cffects, 40.150-151 bility steric effects, 40:153-154 decaisopropylation, a126 electronic effects, 1079-111 decaphenylferrocene, 40.123, 125 Group 2 metallocenes melting points, &127-128 crystal structures, 40.243-244, 246-249 octaphenylmetallocenes of main-group gas-phase electron diffraction, 40.246 metals, &121-122 Lewis base removal, W237-238 oxygen sensitivity, 40:130-132 mass spectrometry, 40246 polyhalogenation, 40:123 physical properties, &239-243 volatility, 40:129-130 stability, 40:236-237 synthetic approaches, 40:120-121 synthesis, 40.237-239 theoretical studies, 1531-34 industrial applications, 40:162-163 transition metal metallocenes lanthanide metallocenes absorption spectroscopy and substitu- molecular mechanics calculations, ent effects, 40:133-135 40:146-147, 149 cyclopentadienyl ring orientation, molecular orbital calculations, 40.146, 40:118-119 148 molecular mechanics calculations, substituent effects, 40139 W135-136 magnetic properties of substituted com- molecular orbital calculations, pounds 40132-133 assay, 40155 structural distortions induced by bulky steric effects, 40:156 substituents main-group metallocenes cobaltocene, a138 gas-phase electron diffraction, 40145 ferrocene, 40:136-138 molecular mechanics calculations, [l]Metallocenophanes, 32164 40:146-147, 149 ring-opening polymerization, 32131-156 molecular orbital calculations, 40.146, [2]Metallocenophanes, 32164 148 hydrocarbon-bridged, ring-opening poly- substituent effects merization, 373156-160 bent metallocenes, 40.140-141, 143 Metallochromans, 13179-181 linear metallocenes, 40.140 isomers, 13181-183 oligomeric metallocenes, &139 Metallocycles, formation of organometallic slipped metallocenes, MI44 compounds, 221-25 183 Metal vapor synthesis

Metallocyclobutanes, 32229-230 Metal-phenylethylene complexes, Metallocyclopentadiene complexes, 38~122-138 5120-122 Metal phosphide derivatives, multiple bond- 1-Metallodiphosphirane, synthesis with ing, 3926-38 phosphaalkenes, 41:6 Metal propargyl complexes, see Propargyl Metalloindanes, 13179-181 complexes isomers, 13181-183 Metals, see also Transition metals; specific Metalloindenes, 13185-190 metals aluminum, 13185 addition of ketenes to form stable com- arsenic, 13185,190 plexes, 2&3 selenium, 13190 basicity, effect on carbene complex reac- silicon, 13190 tivity, 25127-129 Metalloisochromenes, 13190-191 bioamplification, 20:332 boron, 13:190 corrosion in seawater, alkyl halides and, silicon, 13191 3871-74 Metallonaphthalenes, 13191 cyclopentadienyl 0x0 complexes of Metallo-ring systems, 5122-124 Group 3, 28356 Metallotropic rearrangement, in dipallad- Group 4, 28:357 ium complexes, 19170-171 Group 6,28.359-360 Metallovinylketenimine complexes, 32112 Group 8,28358 Metal-metal bond energies, comparison be- graphite intercalation compounds of, tween clusters and surfaces, 12369 28296-97 Metal-metal bonds, 3183-184, 227, 239, alkali, 2892-96 246,251-252, 810-13,10310-311, induction of ketene conversion, 2814-16 1331 M-M’ bond, insertion reactions by Pt(1) bridged by ally1 and cyclopentadienyl li- and Pd(1) complexes, 28283-287 gands, 19156-178 reactions with alkyl halides, 3859, 61-63, cleavage by sulfur compounds, 515-16 65-69 formation by oxidative-addition reac- addition of water, 3870-71 tions, 8:128 Direct Process Reaction, 3867-69, syntheses, 10:36 74-75 theoretical studies, 1537-45 Grignard reaction, 3866-67 dimeric species, 1539-40 surface adsorption of alkyl halides, effect of bridges, 1539 3863-65, 73 Metal-metal distances synthetic, 2893 in bridged electron-deficient compounds, Metal selenolates, multiple bonding, 15237-238 3944-47 beryllium, 15252 Metal silylgermylalkanes, rearrangements, with mixed metals, 15262-266 3986 in organolithium compounds, 15260-261 Metal slurries, via metal atom condensa- Metal-metal triple bonds, 29101-102, 104 tion, 1587 Metal nitrosyls, mass spectra, 6:282 synthetic potential, 15:87 Metal-NR2 bonds, ketene insertion, 285-6 Metal tellurolates, multiple bonding, Metal nucleophile-carbonyl adducts, see Nu- 3944-47 cleophile-carbonyl adducts Metal thiolates, multiple bonding, 3944-47 Metal-OR bonds, ketene insertion, 285-6 Metal-to-ligand charge transfer, nonlinear Metal oxide complexes, reaction with ke- optics effects, 42324-325, 330, 352, 354 tenes, 286-7 Metal vapor synthesis Metal oxoalkyl compounds, 28347-351 arene complexes, 1349 Metal oxoaryl compounds, 28347-351 areneiron phosphine derivatives, 13100 Metal vapor synthesis 184

bisbcnzcneiron (0), 1394 mechanism of transmethylation reactions, organolanthanides, 24154-158 20333-337 Methacrolein, reaction with iminosilancs, of gold compounds, 20336-337 39175 methylation reaction rates, 20315-321 Methane, oxidation to methanol, 38170 bismuth compounds, 20320 Methane complexes, 28.326 lead compounds, 20319 3-Methanediyl-1,3,4,6- mercury(1I) salts, 20316-318 tetraphosphabicyclo[3.1 .O]hex-2-ene, methylmercury compounds, 20:321 synthesis with phosphaalkenes, 4k32 organoarsenicals, 20321 Methanol organornetals, 20321 carbonylation by palladium(I1) acetate, palladium salts, 20319 28185 platinum salts, 20318-319 catalytic carbonylation, 1T255-267 thallium compounds, 2k320 reactions with unsaturated germanium tin compounds, 20:320, 346 coupounds, 39291-292 transition metal ions, 20:320 Methoxide adduct, substitution reactions of, methyl transfer 28173-114 to gold(I), 20103 2-Methoxyallyl halides, in vinylketene syn- to mercury(II), 20103 thesis, U330 to platinum(II), 20103 Methoxycarbonyl, formation, reaction rates to thallium(III), 20103 for, 28168-169 Methylcobalt tetracarbonyl, 4243-244 (Methoxysilyl)sodium, 3820 Methyl compounds, chemical shifts, Methylacetylene, hydrogenation, 28107 U140-141 of Group IVB derivatives, l2167-168 Methylacetylide complex, 3247 1-Methyl-1,1-divinyl-1-silacyclobutane, Methylalkylboranes, 2284 39~45 Methyl anion, molecular orbitals, 27172 Methylcnehoranes, 39:371-373 Methylarsonic acid, 3tk72 Methyleneborates, 39370-371 2-Methylbutadiene, reaction with silenes, p-Methylene complexes, 20159-263 39113, 115 analogy with metal surface species, 2-Mcthyl-1,3-butadiene, photochemical reac- 20228-229 tions with carbonyl complexes bonding of chromium, 26298, 325-328 charge at bridging carbon, 20197, 199 with decacarbonyldirhenium, 26:367 comparison with carbonyl bridging, of molybdenum, 26:299,338-339,345, 20200 347 stabilization by metal-metal bonds, of tungsten, 26299, 341, 351 20199 [(2-Methyl-2-butenyl)diphenylsilyl] cuprate, as dimetallacyclopropanes, 20197, 199 3843 in Fischer-Tropsch chemistry, 20228-231 1-(3-Methylbuten-4-yl)-3-methylborolane, Group IVB analogues, 20231-237 26238 fluxionality, 20235-237 Methylchlorogermanes, 910 structures, 20232-235 Methylchlorosilanes heteropolynuclear compounds, 20184- Direct Process Reaction, 3867-69, 74-75 188, 247 direct synthesis, 96 via earbene addition reactions, use of copper, 9:8 20184-188 Methylchlorostannanes, 910 intermolecular exchange reactions, 202 17 Methykobalamin, 38155 irreversible bridge-opening, 20249 photochemistry, 11:404 mass spectra, 20214-216 Methylcob( 1II)alamin metallation, 20245 185 Methylphenylsilylene

MO calculations, 20197-200 2-Methyllactic acid, in spirocyclic A%-sili- NMR spectra, 2&209-214 cates, ligands, a241 determination of chirality, 20214 Methyl linolenate, homogeneous hydrogena- distinction from carbenes, 20209 tion, 13329-331 metal-metal bond detection, 20212 Methyllithium, 3247 nomenclature, 20161-162 13C NMR spectra, 2142, 169 photoelectron spectra, 20197-1 98 reactions with germanimine, 39:293 protonation, 20223-227 structure, 3370-371 reactions with Methyl manganesepentacarbonyl, 32170 acetylenes, 20219-222 carbonylation, 1k113-115 alkenes, 20222-223 reactions, 32183-206, 213 hydrogen, 20222 with cationic species, 32187-188 similarity to cyclopropanes, 20197 with Lewis acids, 32184-185 stability, 20216 with nucleophiles, 32188-206 structures orthometallation, 32185-187 bridge asymmetry, 20201 with transition metal hydrides, comparison with m-carbonyls, 32183-184 20206-208 structure, 32177-183 comparison with m-vinylidenes, 20208 diffraction studies, 32177-178 metal-metal bonding, 20200 spectroscopy, 32178-182 X-ray data, 2&202-205 synthesis, 32171-175 substitution at methylene bridge, Methylmercuric derivatives, 3871 20218-219 Methyl mercury, see Dimethylmercury synthesis, 20164-197 Methylmetal compounds via acetylene complexes, 20188-190 Group IV, 35, 16 via carbene addition, 20184-188 NMR, 35, 16 from diazoalkanes, 20164, 166-181 Methylmetal derivatives, environmental haz- from dihaloalkanes, 20182-183 ards, 3871 via dimethylmagnesium, 20191 Methylnickel(1V) compounds, 3863 via ketenes, 20:192-193 (E)-Z-Methyl-l,3-~entadiene,in photochemi- via organomercurials, 20192 cal reactions with metal carbonyl com- rearrangement reactions, 20193 plexes via strained hydrocarbons, 20193 of chromium, 26998,327-329 from Wittig reagents, 20183 with decacarbonyldimanganese, 5-Methylenecyclopent-2-enones, synthesis, 26354-355 41:199 of molybdenum, 26:299 2-Methylene 1,2-dihydrophosphete, synthe- (Z)-3-Methyl-l,3-~entadiene,in photochemi- sis with phosphaalkenes, 4k15 cal reactions with chromium carbonyl Methylene radical anion, 15275 complexes, 26:316 Methylidene ruthenium, 29:183 4-Methyl-l,3-pentadiene,in photochemical p-Methylidyne complexes, 20160-161 reactions with metal carbonyl com- NMR spectra, 20213 plexes Methyl isocyanide of chromium, 26:316 reactions with platinum complexes, with decacarbonyldimanganese, 1k77-80 26354-355 reduction by nitrogen-king bacteria, Methylphenyldisilylbenzenes, photolysis, 1k53 3999 2-Methyl-5-isopropyl-1,3-cyclohexadiene,in Methylphenylsilylene, addition reactions photochemical reactions with chro- to 1,3-butadienes,1968 mium carbonyl complexes, 2&316 to carbon-carbon double bonds, 1961-65 Methylphenylsilylene 186

cyclic olefins, 19:62-63 organocobalt complexes, 1k421 internal olefins, 1962-63 Methyltrioxorhenium(VI1) Methylpotassium, crystal structure, 22192 absorbance spectroscopy, 4k130, 132 Methyl propargyl ether complex, 3253 alkene epoxidation, catalysis with hydro- 2-Methyl-2-propenyl-N-(2,6- gen peroxide diisopropylphenyl)imine, 39180 hydrogen peroxide adducts, 4k130, Methyl radical, reaction with Ge hydrides, 132-133, 137 44:86,88 kinetics, 4k133-134 Methyl rheniumpentacarbonyl, 32170 oxygen atom transfer, mechanisms, reactions, 32206-213 4k134-141 with cationic species, 3%207-208 substrates, 4k130 with Lewis acids, 32207 alkyne oxidation, 4k141 with nucleophiles, 32208-212 Baeyer-Villiger oxidations, 4k142 orthometallation, 32207-208 bishydroxylation of alkenes with transition metal hydrides, 32206 cycloreversion of rhenium diolates synthesis, 32175-177 crystal structure analysis, 4k1.50 Methylruthenium(I1) complexes, 29175 kinetic isotope effect, 4k151-152 1-Methyl- I-silacyclobutane, pyrolysis, 3992 molecular orbital calculations, 2-Methyl-2-silaindane, 39142 4k154-156 Methy Manes thermodynamics, 4k148-154 acidity, 9277 importance in organic synthesis, methylation of styrene via palladium(II), 4k142-143 19224 mechanisms, 4k143-144 1-Methylsilene 0x0 ligand migration, 4k144-148 and dimethylsilylene, interconversion, crystal structure, 4k132-133 2336 oxygen insertion into aliphatic bonds, IR spectroscopy, 39:lOO 4h142 Methylsilicon(I1) chloride, 3868 physical properties, 4k129 Methylsilylene, reaction with silene, quinone synthesis, conversion from ar- 39138-139 enes, 4k141 Methylsodium, crystal structure, 22191 synthesis, 4k128-129 Methylsulfonium salts, in transmethylation, 1-Methyl-1-N,N,N’-tris(trimethylsily1) 20322 ethylenediamino-2-neopentylsilene, Methyltechnium trioxide 39141 alkene epoxidation, catalysis, 4k130, 135, Methyl vinyl ether, 39178 137,139 Methyl vinyl ketone, reaction with silenes, oxidation reactions, 4k142, 148 39125 synthesis, 4k128 1-Methyl-1-vinylsilacyclobutane,3992, 145 Methyltin halides, 1463-96 Methylvinylsilene, 3992, 145 molecular complexes, 1476-92 Methylyne, ligand conformation, 23163 spectral studies, 1464-67 Meyer reaction, 4148-149 structural studies, 1468-76 Mg/MgBr2, tetrahedrane synthesis, 326-8, Methyltin trihalides, 1472-76 23,26-27 electron diffraction studies, 1472 [M( T~-C~H~)~],third-order nonlinear optics molecular complexes, 1490-91 of rare earth complexes, 43371 NMR data, 1474-75 MH, compounds, structure and bonding NQR data, 1474 SiH2, 33135-140 structures, 1472-76 SiH3, 33135-140 Methyl transfer reactions Michaelis condensation, 4149 cobalt-containing enzymes, 1k439 Microwave spectra 187

difluoromethylarsine, 421 1 of carbonylhydrides with hydrogen, dimethyl sulfide, 540 18254 organosilicon pseudohalides, 5191 related linear polynuclear carbonyls, trimethylarsine, 4:210-211 18265-267 Migration ruthenaferraboranes, 3333 carbonyl ligands, 16319, 323-332 stereochemical nonrigidity of carbonyls, hydride ligands, 16319,332-336 18208,257-269 in tetracoordinated organoboranes, NMR studies, 18257-264 1682-91 tetranuclear, 18259-260 chemical induction, 1682-84 trinuclear, 18258-259 with deboration, 1688-91 synthesis, 18209, 227-242 photochemical induction, 1684-88 via addition to coordinatively unsatu- thermal induction, 1682-84 rated species, 18230-233, 240-241 unsaturated organic ligands, 16319- via addition to metal acetylides, 18239 336-16341 bridge-assisted reactions, 18240 Migratory insertion reactions photolysis, 18237-238 computer representation, 26177, 188-189 pyrolysis, 18227-230 feasibility matrix, 26188 via reaction between carbonyl anions dihalo and monohalocarbene complexes and metal halides, 18236-238, 241 of Ir, Os, and Ru, 25180 redox condensation, 18233-236,241 Mixed-metal clusters, 18207-273 scrambling of carbonyl anion clusters, auraferraboranes, 3333 18238-239 auraruthenaboranes, 3333 strategy, 18239-242 carbonylation, 18254-255 triosmium, %70-81 deprotonation of carbonylhydrides, Mixed-metal compounds, alkali metal organ- 18253 ics, 22208-235 electronic spectra of carbonyls, 18246 Mixed-metal organomagnesium complexes as heterogeneous catalyst precursors, main group metals 18207-208, 257 aluminum, 32204,208 to dispersed bimetallic species, 18257 lithium, 32203-208 high-pressure liquid chromatography, magnesate units, 32203-207 18248-249 sodium, 32203-205,207-208 as homogeneous catalysts, 18207-208 transition metals for hydrogenation, 18256 cobalt, 32209 for norbornadiene dimerization, 18256 copper, 32208-209 for water-gas shift reaction, molybdenum, 32210-211 18256-257 nickel, 32:209-210 IR spectroscopy, of carbonyls, MLEV pulse sequence, 2&424 18245-246 MM2 force field, 36130, 133 ligand substitution, 18250-253 Mn(CO)S., 3354, 56,63, 65-67 listing, 18210-226, 268-269 [(p-~’:$~Se=CH2)(Mn(CO)2(~5-CsH4Me)]], mass spectra, 18242-244 synthesis, 43172 chemical ionization, 18:244 [(~L-~~:~-E=C~~,)IM~(CO)Z(~~’-CSM~S)J~I, Mossbauer spectra, 18247-248 synthesis, a172 NMR spectra of hydrides, 18247 [Mn(CO)*( V’-Se=C(Ph)H)( $-CsHs)], protonation of carbonyl anions, cycloaddition reactions with conjugated 18253-254 dienes, a181 reactions (Mn(CO)SJ&-GeH2), synthesis, 42253 with acetylenes, 18255-256 [Mn( CO)2(S=C( C6H4R-pP)(CsH4Mn- Mobility 188

(CO)-J}(T~-C~H~)],v'-E/q'-Z isomeriza- comparison of theoretical models, tion, 43134 196-14 [Mn( CO),(S=C(Ph)[ ( q5- developments of new concepts, C,H,)Mn(CO),])(q'-C5H5)l,synthesis, 15 12- 14 43: 141 interpretation of spectroscopic results, Mobility. bridging ligands in trivsmium clus- 156-10 ters, 2658-61 molecular geometry, 1510-11 alkyne rotation, 2661 organometallic reaction pathways, carbonyl migration, 2660 1511-12 enantiomerization, 2659 on complexes of boron heterocycles, fluxionality, 2660 18305-307,313,320 hydride mobility, 2658-59 for coordinated acetylenes, 16246-247 nuclear inversion, 26:60 cycloreversion of rhenium diolates, phenyl motions, 2660-61 4k154-156 vinyl ligands, 2658 derived from Mossbauer spectroscopy, Mobility, silicon, organosilicon 1,2-anionic 9:87 rearrangements, 161-2 of 1,4-diaza-1,3-butadienes,21:154 [MoCl(p-O-tpph,)(NO)(HR(dmpz,)l. sec- metal complexes, 2k172-173 ond harmonic generation, 42319,321 on dinieric organo-Group 111 derivatives, Mo,(CO),AsRPh,, structure and bonding 16:113-115, 126 factors, 4275 on dinickeltricyclopentadienyl cation, 18306-307 [Mo(CO)dEt)($-S=C(Avl)z)( q5-CgH5)], synthesis, 43177 and ESR spectra of Group IVB radical Molecular orbital analysis anions, 15286 [Fe2(CO),STe2(p-HC=C(C= CMe))], ferrocene, 40132-133 4k2&3,289 main-group metallocenes, 40146,148 ferrole complexes, 2338 nineteen-electron organometallic radicals, formyl complexes ligand substitution and atom abstrac- and hydride migration, 2031 tion, 40:202-203 ligand geometry, 2015 Molecular orbital calculations, 152-14 p-germylene complexes, 20234-235 and alkyl migration to CO, 23280 on high nuclearity metal carbonyl clus- alkynyl-metal complexes, 3883-84 ters, 14539-341 arenemetal orbital calculations, 135-55 for ligand bridged dipalladium com- 1457 on azobenzene, pounds, 19:168-170 and n-bonding, 16242-243 linear combination of atomic orbitals boranes methods, 152-5 iron carbonyl complexes, 2k73-75,77- CNDO methods, 155 79,85-86,98 Hiickel approximations, 194-5 manganese tetracarbonyl, 2k88 self-consistent field calculations, 153-4 triborane, 2k77 Wolfsberg-Helmholtz approximations, on boron hydride derivatives, 14147 15:4-5 on bridged electron-deficient compounds, manganese compounds 15237 of aminyl radical, 23:51 and carbonyl isocyanide oxidation, 2310, of butadiene, 2338 23 carbonyls, 2319 chromium carbenes, 238 p-methylene complexes, 20197-200 cobalt-alkyne complexes, 41:7Y, 81, 90 for methylene group on Ni(11l) surface, cobalt dime radicals, 2362 20228 C,O-bonded carbonyls, 23239 on organometallic nitroxides, 16:18-19 189 Molybdenum carbonyl diazene complexes

on phosphorus ylides, 14212 mixed-metal clusters, 18210-211 platinum acetylene and olefin complexes, tantalum halides, 18210, 227-228 13~303-304 platinum heteronuclear cluster, and redox-induced isomerization, 2316, 31:380-382 62 reaction with benzyl bromide, 3873 rhodium cyclopentadienyl carbonyl, 2359 tetracarbonylmetallate(4-) anion, self-consistent field-X,-scattered-wave cal- 31:39-45 culations, l55-6 tetraki~(.r)~-allyl),13C NMR spectrum, titanium o-phenanthroline derivatives, 19280,282-283 2344-45 Molybdenum alkoxides, 22311-369 Molecular orbital perturbation theory, carbonyl complexes M159-160 molecular orbitals, 22361-362 Molecular orbitals structure, 22359-360 alkynylaluminum complexes, 26241 synthesis, 22359-360 cyclopentadienylberyllium complexes, dinuclear alkyl and aryl complexes 26229-230 reactions, 27:351 cyclopentadienylgermanium complexes, structure, 22347-348 26261-262,264-265 synthesis, 22344-346 cyclopentadienyllithium, 26222 dinuclear alkyne complexes dicarbollylgallium complexes, 26246-247 reactions, 22340, 343 dicyclopentadienylgermanium complexes, synthesis and structure, 22337-339 26273 metallacyclobutadiene complexes, dicyclopentadienyllead complexes, 26273 22332-333 dicyclopentadienylmagnesium, ring expansion, 27:336-337 26:234-235 structure, 22334 dicyclopentadienyltin complexes, mononuclear alkylidyne complexes 26272-273 reactions, 22325-328 dihydridodecacarbonyltriosmium, 265 synthesis, 22321-322 dimetallacyclobutadienes, 26100-102 Molybdenum, anionic hydride complexes methyl anion, 22172 as catalyst, 2245 mixed-metal triosmium compounds, 2675 reactions, 2228-29 molybdenum and tungsten alkoxides, with Bransted acids, 2233-34 22316, 361-362 with ketones, 2243 v5-pentadienyl-transition metal com- spectroscopic properties, 224-7, 23 plexes, 26157 structural characteristics, 2212-16, 18-19 pentadienyltricarbonylmolybdenum com- Molybdenum carbonyl compounds plexes, 26152 anions containing cyclopentadienyl, trimethylenemethane metal complexes, 2190-202 22291-294 dianions, 2182-184 Molecular orbital theory hydrides, 2200-202 of n-ally1 transition metal complexes, miscellaneous anions, 2188-190 2333-335 monoanions, 2:185-186 of hydrocarbon anions, 2132-135 nitrosyl derivatives, 2199-201 Molecular oxygen carrier, 3245-246 Molybdenum carbonyl derivatives, Molten salts, in hydrogenation catalysis, 3196-213 12368 chemical shifts, 12:174, 191 Molybdenum, see also Group VI metals Molybdenum carbonyl diazene complexes cyclopentadienylcarbonylatein phase bisdiazenes, M80-81 transfer catalysis, 19189 dimetallacycles, M89-90 mixed alkali metal compounds, 22251 electrochemical reduction, 3492-93 Molybdenum carbonyl diazene complexes 190

IR studies, 3483 absolute configuration, 18193-194 NMR studies, 3482 asymmetric synthesis of aziridine deriva- photochemistry, 3490 tives, 18187 preparation, 3480-81 of optically active aminophosphines, thermal reactivity, 34:90 18167, 180-181, 194 uv-vis spectrum, a85 optical purity, 18167 Molybdenum carbonyl diazirine complexes, optical resolution of Schiff base deriva- 3481-82, 86 tives, 18: 163- 165 Molybdenum carbonyls, substitution mecha- square-pyramidal, 18177-181, 188-189 nisms Molybdenum complexes, 39:53 hexacarbonyl derivatives acyclic pentadienyl CO dissociation rate parameters, q5-pentadienyltricarbonyl anion, 21:117 26:151-152 of diazobutadienes, 2k136 structure, 26136 of diphos, 2k142-143 synthesis, 26154 effect of hydroxide, 2k138-139 alkyl, 38108 and isomerization. 136-137, 21:141 alkylamides, 22153 ligand competition, 21:115 and catalytic decomposition of formic pentacarbonyl amines, 2k127-130, 137, acid, 22141-142 140 alkylidene carbaborane, 3k64-65 of phenanthrolines, 2k143 gold, 3159 ligand steric requirements, 2k119-122 alkynyl, 3885, 100, 108, 115 in cis(bis ligand) complexes, allenyl, 37:118 21:119-120 allyls X-ray structural studies, 2k119-120 nonngidity, 16228-230 tetracarbonyl norbornadiene, 2k132-135 u-TIrearrangement- 16244-245 "CO substitution, 21:133 arene, 1363-65,67-70,82-90 tricarbonyl arenes, 2k123 assisted carbonyl insertion reactions tricarbonyl cyclopentadienyl radical, by alumina, 23284 21:143 by Lewis acids, 23284, 287 tricarbonyl trienes, 2k135-136 binuclear n-C,O-bonded carbonyls, Molybdenum, carbyne complexes 23273-275 as catalyst in alkene metathesis, 2290 niobium derivatives, 23272-273 reactions zirconium derivatives, 23271-272 with acetylenes, 2R93-94 borane, 21:63-64, 104 with acids, 2279-80 butadiene with carbon monoxide, 2299 "C NMR spectra, 19:275-276 carbyne coupling, 2284 structure of tns-complexes, 19:275 with chalcogenides, 2295 carbamoyl, 1827-28 with Lewis acids, 2282 carbonylation, 1k89, 100-102, 118-121 with metal complexes, 2288 carbonyl-( v5l-cyclopentadienylethyl)( q4- with nucleophiles, 2272-76 diene), 26340 photolysis, 27:98 cyclopentadienyls, 30:216-217 transformation to vinylidenes, 27:95-97 substituted, 2k9-10, 12, 36 with xylylisocyanide, 27:99 dicarbonylbis-( q4-diene) spectroscopic properties, 2756 dynamic behavior, 26:314-315 structure, 2254 stereochemistry, 26311-313 synthesis, 2257-58, 62-68 dicarbonylcyclopentadienyl dimer, Molybdenum, chiral cyclopentadienyl com- 23:273-275 plexes bonding, 23273-274 Molybdenum(1l) complexes

reaction with diazoalkanes, 20180-181 vinylidenes, 2266-68, 88-89, 100, dicarbonyl( ~s'1-cyclopentadienylethyl)-~2- 104-105 diene, 26339-340 carbyne formation, 22:73 disilene, 39269 Molybdenum complexes, electron-transfer formyls, 20:6, 10 reactions q4diene carbonyl, 2k299 allyls, 2378 diene ligand rotation, 26:305, 308-310 arenes, 2365 synthesis, 26300 aryls, 23:34 heteronuclear n-C,O-bonded clusters, carbonyl derivatives 23276-278 carbenes, 238-9 via metal atom synthesis, 1592-93 cyanides, 239 nitrido clusters, 2463, 66, 70, 72-73 dithiocarbamates. 2317 nitrosyl clusters, 245, 51-54 halides, 2318 mixed metal derivatives, 2448, 51-53 isomerizations, 234, 9-10 olefin derivatives, nonrigidity in, of N-donors, 23:12-13 16227-228 of o-quinones, 2317 in olefin metathesis, 16284 redox potentials, 236-7 organolithium derivatives carbonylphosphines, 23:13-17 binuclear methyl, 2397-398 isomerization, 23:15-16 bis(cyclopentadienyl)dimethyl, oxidation YS. substitution, 2314 W.276-277 oxidative addition, 23:17 nitrosyl cyclopentadienyls, 24:334-335 cyanoarene derivatives, 24101-102 pentacarbonyl cyclic carbene deriva- cy clohept atrienyl , 2366 cyclopentadienyls tives, 24:329-331 tricarbonylcyclopentadienylalkyls, alkyls, 2348 alkynes, 23:47-48 24280-287 carbonyls, 23:47-48 phenylethynyl, 38122, 135-136 nitrosyls, 2349 ProPargYI of S-donors, 2348 dinuclear complexes from, 32242 diazoalkanes, 2312 structure, 3283, 86 reduction to amines, 2312 reactions with isocyanides, 1k30 of dinitrogen, 2311-12 silylmethyl derivative, 11:317 halide-bridged tropylium compounds, sulfur dioxide insertion reactions, 24101-102 U60-61 isocyanides, 23:lO-11 terminal Z-C,O-bonded carbonyls isomerization, 2377 with aluminum derivatives, 23238-240 redox potentials, 236-7, 9 with magnesium ions, 23235-237 ligand-bridged carbonyls, 24100-102, 122 with titanium cyclopentadienyls, 23:244 mediation by CO ligands, 23296 with zinc alkyls, 23243 mixed metal clusters, 24:111-112, 116 with zirconium cyclopentadienyls, pyrrazolyl borates, 2378 23242-243 sandwich compounds, 2369 thallium, 3953 Molybdenum(I1) complexes tricarbonyl CI1and Ci4. 26331-333 alkyne ligands, reaction in d4 monomers tricarbonylcyclopentadienyl, migratory in- alkyne insertion products formation, sertion reactions, 26:189 29~83-90 tricarbonylcyclopentadienylmethyl, metal-alkyne cleavage reactions, 26336-346 29:90-92 tricarbonyl-+dienebis( $- q2-vinyl ligand formation, 2971-83 methylcyclopentadienyl), 26547-350 alkynes, structures, 29:23-24 Molybdenum(l1) complexes 192

bisalkynes, 2932-34 oxygen donor ligands, &82,84 CpMol(RCE CR)X, 2930-32 phosphorus donor ligands, &81-82 Mo(CO)(RC=CR) LX2,2924-28 seven-coordinate halocarbonyls, Mo(L)(RC=CR)(B-B),, 2928-30 40637 bisalkyne complexes sulfur donor ligands, &82, 84 alkyne rotational barriers, 2960-61 synthesis, &77-78,87-91 IR spectra, 2957, 59 a-ally1 complexes Cp(CO)ZMoECR, 293 catalytic activity, &98 CpMo(RC= CR)LX, synthesis, 299-12 crystal structures, &92-93, 96-97 CpW(RC=CR)LX syntheses, 299-12 reactions with donor ligands cyclopentadienyl alkyne derivatives, syn- arsenic, &95 thesis, 299-12 bidentate, &96 d4 alkyne carbon, &94 electrochemistry, 2969-71 nitrogen, &95 electronic spectra, 2964-68 phosphorus, &95 IR spectra, 2962-64 synthesis, &91-94 internal bisalkyne complexes, 2959 arene complexes internal monoalkyne complexes, crystal structure, &lo4 2947-51 synthesis, 40:103 terminal alkyne complexes, 2944-47 r17-cycloheptatrieny1complexes, 40.104 terminal bisalkyne complexes, 2958 cyclopentadienyl and related complexes d4 alkyne monomers, synthesis of, 296-7 isomerization, 40:102-103 four-electron alkyne ligands, 291-3 reactions with neutral donor ligands, mixed alkyne-olefin d4 complexes, isola- 40.102 tion, 298-9 synthesis, &101-102 Mo(CO)(RC=CR) LX,, synthesis, diene complexes 29~6-7 conjugated complexes, 40:98-99 Mo(CO)~(S~CNE~&,297 crystal structures, 4098-100 monoalkyne complexes, alkyne rotational nonconjugated complexes, &99-101 barriers, 2951-57 history of study, &46 Mo(RC= CR)Z(S2CNEt2),,synthesis of, six- and seven-coordinate complexes 2914-16 acyl complexes, synthesis, &73 Mo('ITP)(PhC=CPh), 2913 anionic oxygen/sulfur donor ligands NMR spectra and synthesis, &73-74 internal bisalkyne complexes, 2957, 59 bidentate nitrogen donor ligands, terminal alkyne complexes, 2944-47 &50-51 terminal bisalkyne complexes, 2957-58 catalytic activity, 40:74 Molybdenum(II), halocarbonyl complexes crystal structures, &48, 51-53, 57-58, alkylidene complexes 68,73-74 crystal structures, &75-76 halides as oxidizing agents, &67-69 synthesis, &75 intramolecular oxidation of zero-valeni alkyne complexes complexes, &69-70 crystal structures, &78-79, 81, 87-88 iodine compounds as oxidizing agents, reactions &67 Ag[BF4], &85 metal carbonyl fluorides, synthesis, anionic donor ligands, &84 &70-71 carbon donor ligands, &79-80 metal halocarbonyls, reactions with 1,8-~yclotetradecadiyne,&85-86 neutral donor ligands, &71-72 1,4-diphenylbutadiyne, &86 photochemical oxidation reactions, nitroeen donor lieands. 40:80-81 &66 193 Monocyclic zwitterionic A5Si-silicates

seven-coordinate complex, reaction phosphines, 22232-233 with donor ligands redox reactions, 22255-257 alkyne reactivity, 4087 reductive coupling, 22257 antimony, &62 thiolate, 22232 arsenic, M62 Molybdenum, main group complexes bidentate nitrogen-sulfur, 40:64-65 antimony and bismuth, 3k130-137 bismuth, 4061-62 gallium, indium, and thallium, 3k92-96 nitrogen, 4058-59 germanium, tin, and lead, 3k108-113 oxygen, M62, 65 tellurium, 3k155-157, 169-171, 175 phosphorus, 4059-62 Molybdenum, trimethylenemethane com- sulfur, 40:63-65 plexes structural geometry, &47-48 reactions, with nucleophiles, 22295-297 synthesis with structure, 27:289, 292 bidentate phosphine ligands. synthesis, 27:284 4054-55 Monoalkyne complex syntheses butylisonitrile, 4050 CpMo(RC=CR)LX, 299-12 halide ligands, 40:48-50 ML(RCE CR)(B -B)Z, 29:7-9 monodentate nitrogen donor ligands, Mo(CO)(RC=CR)L>Xz, 296-7 4050, 56 Mo(I1) alkyne complexes with other stoi- monodentate phosphine ligands, chiometries, 2912-13 4053-54 (RCZCR)LX, 299-12 oxygen donor ligands, 4055-56 W(CO)(RC=CR) LX,, 296-7 seven-coordinate complex synthesis, W(I1) alkyne complexes with other stoi- 4056-58 chiometries, 2912-13 sulfur donor ligands, 40:56-58 Monoamines, multiple bonding, 3918-26 tridentate nitrogen donor ligands, Monoarsaferrocenes, 39:332 40:51, 53 Monoarsenides, multiple bonding, 3926, 28, synthesis with, arsenic donor ligands, 37-38 4055 Monoarylhalides, types, M23-25 Molybdenum cyclopentadienyl tricarbonyl Monoaryloxides, 3939 derivatives, 2190-202 Monobismaferrocenes, 39332-333 Molybdenum, 1,4-diaza-1,3-butadiene com- Monocarbonyl derivatives plexes, 2k136 hafnocene, (q-CsMe& Hf(H)*(CO), for- allyl, 21:160-161, 168-169, 171-1 72 mation, 25372 bonding, 21:172-175 titanocene conformational stability, 2k176 monocarbonyl q2 acetylene complexes, ligand activation, 2k228-229 formation, 25358-361 with monodentate ligand, 21:165 monocarbonyl-q*- olefin complexes, for- radicals, 21:213, 217 mation, 25361-363 solvatochromism, 2k174 monocarbonyl-phosphine complexes, tetracarbonyl chelate, 2k168-171 25351-358 Molybdcnum, isocyanide complexes, 1k49- zirconocene 51,22251-252, 261,263-264 monocarbonyl-phosphine complexes, alkylation, 22295 25365-366 allyl, 22232 other derivatives, formation, carbonyls, 22:217-218, 225-227 25366-371 cyclopentadienyls, 22226, 230, 243, 257 Monocyclic zwitterionic A%-silicates eight-coordinate cyanides, 22216, 243 with SiO2FCZskeleton halide, 22232 NMR studies, M266, 268-269 homoleptic species, 22:221, 243 synthesis, a266 Monocyclic zwitterionic h5Si-silicates I 94

X-ray diffraction studies, M266 modification of carbyne complexes, synthesis, a228 25172 Monocyclopentadienylberyllium complexes, modification of monohalocarbene li- 26228-231 gand-containing complex, 25172 bond distances, 26:229 oxidative addition of [Me,NCCI2]CI, fragment orbitals, 26:229-230 25172 ionization potentials, W231 ruthenium orbital energies, 26:231 "C NMR, 25175 preparation, 26228 IR spectroscopy, 25175-176 structures, 2k228 metallacycle formation, 25:179-180 Monocyclopentadienyllead complexes, migratory insertion reactions, 25180 26280-281 reactions with electrophiles, 25180 Monoenes. diene hydrogenation to form, reactions with nucleophiles, 25176-179 3tk171-172 structure Monohalocarbene complexes carbene ligand orientation, 25175 iridium carbon-halogen bond, 25173 ''C NMR, 2517.5 metal-carbon bond, 25173 IR spectroscopy, 25175-176 trans influence, 23175 metallacycle, formation, 25179-180 synthesis migratory insertion reactions, 25180 modification of adihaloalkyl deriva- reactions with electrophiles, 25180 tives, L, M =CX2R, 25171-172 reactions with nucleophiles, 25176-179 modification of carbyne complexes, structure 25172 carbon-halogen bond, 25173 modification of monohalocarbene li- metal-carbon bond, 25173 gand containing complex, 25172 oxidative addition [Me,NCCI,]CI, trans influence, 25175 of synthesis 25172 pMonohalogenoalkyl transition metal com- modification of adihaloalkyl deriva- plexes tives, L, M-CX2R, 25171-172 cobalt compounds, 33282 modification of carbyne complexes, iridium compounds, 33279-280 25172 iron compounds, 33278-279 modification of monohalocarbene li- manganese compounds, 33:273-275 gand containing complex, 25172 molybdenum compounds, 33:273-278 oxidative addition of [Me2NCCI2]Cl, platinum compounds, 33:280 25172 rhenium compounds, 33:279 osmium rhodium compounds, 33283 I3C NMR, 23175 ruthenium compounds, 33279 IR spectroscopy, 25175-176 tungsten compounds, 33273,277 metallacycle formation, 25179-180 Monohalogenomethyl transition metal com- migratory insertion reactions, 25180 plexes reactions with electrophiles, 25180 chromium-halomethyl, 33242-243 reactions with nucleophiles, 25176-179 cobaloxime-halomethyl, 33251 structure cobalt-halomethyl, 33248-250 carbon-halogen bond, 25173 cobalt-porphyrin, 33251 metal-carbon bond, 25173 gold-halomethyl, 33271-273 trans influence, 25:175 iridium-dihalomethyl, 33259 synthesis iridium-halomethyl, 33:257-258 modification of a-dihaloalkyl deriva- iron-chloromethyl, 33236-237 tives, L, M-CX2R,25171-172 iron-iodomethyl, 33237, 240-241 195 Mossbauer spectroscopy

iron-methoxymethyl, 33236-237 Mossbauer resonance, of iron carbonyl com- iron-triphenylphosphine, 33239 plex, k6-7 iron-ylide, 33237-238 Mossbauer spectra manganese-halomethyl, 33246-247 iron complexes, mixed-metal clusters, molydbenum-cyclopentadienyl analogs, 18247-248 33245 of 1,2,5-thiadiborolenes, 18312 osmium-hydroxymethyl, 33241 metal nitrosyl complexes, 2234 palladium-halomethyl, 33259-260 mixed valence ferrocenyl derivatives, platinum-chloromethyl, 33261-265 2489 platinum-halogen bond, insertion, 33269 tetranuclear iron clusters, M115 platinum-halomethyls, 33266 Mossbauer spectrometry platinum-ylide, 33262-263 europium (15*Eu),9380 rhenium-formyl, 33247 organotin compounds, R21-134 rhenium-halomethyl, 33247 characteristics of n9mSn isotope, 926, rhodium-halomethyl, 33251-257 46-50 ruthenium-chloromethyl, 33240 general considerations, 945-50 tungsten-cyclopentadienyl,33:246 isomer shift, 950-59 tungsten-iodomethyl, 33244 complex formation, 953-56 Monohydrido(arene)ruthenium, preparation nature of ligand, 956-57 from ruthenium(I1) complexes, valence state, 952 line asymmetries, 978 29176-177 119"'Sn data for organotin compounds, Monohydrido osmium complex, 29197 9106-134 Monohydridoruthenium(I1) complexes, 'lgmSnrecoil-free fraction, 976 29177-178 thermal neutron capture, 957-58 Monolithioferrocene, 32136 Mossbauer spectroscopy Monomethylbenzosilacyclobutane, 39142 alkynyl-metal complexes, 38239 Mono-p-hydrido trichloro complex, 29:196 calibrations, 9:32 Mononuclear complexes, M(C&)X'LZ, electric field gradient, 971-74 28:229-232 asymmetry parameters, 9:72 Monoolefin-iron tetracarbonyls, k35-36 experimental techniques, 9:29-32 Monoolefins, palladium(I1) catalyzed reac- general principles, 923-33 tions, see Palladium(I1) catalyzed reac- heteronuclear clusters, 29304, 306-307 tions isomer shift, 935-38 Monophosphaferrocenes, 39332 relation to NMR coupling constants, Monophosphides, multiple bonding, 958 3926-38 line asymmetries, 943 Monosilabenzene, properties, 39101-102 line width, 944 Monosilyldiazene, thermolysis, 23146 magnetic splitting, 941 Monosodium acetylide, crystal structure, organotin(I1) compounds, 19:130, 22195 134-135 Monostibaferrocenes, 39332-333 a-bonded organostannylene, Monosulfonated triphenylphosphine, see 19142-143 TF'PMS transition-metal derivatives, 19148-149 Monothiolates, 3946 parameters, 934-45 Monsanto acetic acid process, 3544-45 quadrupole splitting, 938-40, 59-71 Moore-type cyclization, synthesis of indo- molecular symmetry, 9:74 lines, 4k210-211 origins, 959 Mossbauer effect, see Mossbauer spec- in various compounds, %60-61 troscopy recoil-free fraction, 942 Mossbauer spectroscopy 196

resonance effect, 942 N substituent effects on metallocenes iron-57 spectra of ferrocenes, NaC(C5H4N)Ph2.PMDTA.THF,structure, 40:157-160 43280 tin-119 spectra of stannocenes, [Na(CSH5);, synthesis and structure, 43297 40.160-161 NaC5H5, structure, 43294-295 temperature dependence, 944 NaC6H3(CH2NMe&, synthesis and struc- I9’Au Mossbauer spectroscopy ture, 43293-294 organogold(1) compounds, 20:67 Na2[C20H12].4diglyme,structure, 43329-330 ylidegold complexes, 2097-98 Na2[C20H12].4DME,structure, 43329-330 and oxidation state, 2099 NaC16H,,.Et20,synthesis and structures, Mossbauer studies, methyltin halides, 43328-329 1466-67,69,71-72.74 [Na(C,H3Mesz-2,6)],, structure, 43292-293 molecular complexes, 1485-87, 89, 91 NaCSHPh4.DME,structure, 43:301 [Mo(T~~)(CO)~[S~F&,synthesis and struc- [NaCH(SiMe& synthesis and structure, ture, 41:245-246 43280, 283 [MSC6H3-2,6-(2,4,6-’Pr3C6H2)2],synthesis Na(p-$, q5-C5Hs)Sn($-C5H&.PMDTA, and structure, 43334-335 synthesis and structure, 43297, 299 Mullikcn’s charge transfer theory, 34149- Na2[CzoH12].2tetraglyme,structure, 151, 160 43329-330 Mulliken’s formula, intrinsic bond energies, NaCsMes, structure, 43301 2: 108- 109 NaC(SiMe.3)(SiMe2Ph)2.TMEDA, synthesis Multinuclear NMR spectroscopy, and structure, 43286 28442-445 NaC(SiMe3)2(SiMe2Ph).TMEDA,synthesis Multiple bonding, 391-4 and structure, 43286 alkoxides, 3939-44 [Na(DME),12[Ph2CC=CCPh2],synthesis aluminum, 392 and structure, 43:315, 317 amidc derivatives, 3918-26 [Na(Et&)~l[F~~W~T~R(T~M~)(CO),~]~H~O, arsenide derivatives, 3926-38 synthesis and structure, 4k250-251 aryloxides, 3939-44 Naked-nickel catalysts, 850 bond lengths, 394-6 oligomerization of butadiene, 880-82 boron-carbon, 39355-388 NaLi(4-MeC6H3CH2NMe),synthesis and diamides, 39:18-26 structure, 43273-214 diphosphides, 3926-27, 35, 37 [Na(Me3SiNCHNCHNCHNSiMe3)]3,syn- disilenes, stable, 39239 thesis and structure, 43324 gallium, 392 Na[PhCHNCHPh].PMDTA, synthesis and Group 3 elements, 3913-47 structure, 43320, 323 indium, 392 Naphthalene phosphorus, 39193-194 adduct with antimony trichloride, 26284 selenolates, 3944-47 radical anions of Group IVB derivatives, silenes, 3972 15291 silicon-arsenic, 39193-195 reduction reaction, 38:14 silicon-phosphorus, 39193-195 Naphthalene-2,3-diolato(2-) bidentate li- tellurolates, 3944-47 gand, in spirocyclic A%-silicates thiolates, 39:44-47 nb irritio studies, 4232-233 transition metal derivatives, 3947-62 chemical properties, a235 9,lO p rule, k284-286 geometry optimization, 44:232-233 Mutual exclusion rule, k249, 255 NMR studies, M233-234 Mycological methylation, arsenic com- synthesis, a230 pounds, 4173 X-ray diffraction analysis, 44:230-233 197 Nickel

Naphthalynes, transition-metal complex syn- to unsaturated metal-metal bonds, thesis and reactivity, 42:178-181 18231-232 Naphthyl, bridging ligand, 1916 alkyl halide adsorption on, 3863-64 Na4[rubeneJ4.THF, synthesis and structure, asymmetric synthesis of bis(a-pinenyl) 43330-331 complex, 18187-188 [Na(THF)3(m-h5, h5-C8H8)Ce(C8H8)], syn- catalysts, 849 thesis and structure, 43318-319 in catalytic complex, 26189 Natural product synthesis in catalyzed butadiene oligomerization via butadiene telomerization, 12182-189 "C NMR spectra of intermediates, via catalytic hydrogenation 19286-288 by rhodium phosphine complexes, cyclotrimerization, 19286-287 12325-327 dimerization, 19287 by ruthenium complexes, 12326-327 catalyzed olefin isomerization, by phos- via nickel metallacycles, 17:204 phite complex, 16260-262 via organonickel complexes in catalyzed synthesis of Li[AIHEt3], and carbonylation, 17:232 19110 and cross-coupling, 17:209-215 cyclododecatriene-bis-phenyllithiumcom- [N(AUL)~J'+,structure and bonding factors, pound, 19.101-102 42:37, 40 dicyclopentadienyl, reaction with Lewis NaYb(C,H&, synthesis and structure, bases, 19156 43299 effect in Ziegler-Natta catalysis, 1997-99 Nb-benzyne complexes, synthesis, ethylene phenylsodium compounds, 42167-168 19102-104 (NBu4)? [MZ(p-Br)ZBr4complex, arylation high nuclearity carbonyl clusters, 14287 of, 28226 reactions, 14333-334 (NBU~)~[M(~-X)(C~X~)~]~complexes, syn- structural data, 14287-298 thesis of, 28240-243 synthesis, 14:333-334 (NBu4)n[ChC1s)ZPt(m-C1)2Ag]n,polymeric hydrocomplexes, 13:273-361 and derivatives, 28263-266 in metallacycles, 2697 Neocarborane, 365, 13 mixed alkali metal compounds, 22211- Neocarborane (1,7-dicarbaclovododecabor- 215, 249,252 ane(12), 3318, 335-336 mixed-metal clusters, 18:15, 211-213, derivatives, 3353 216-217,220,223-226 Neodymium complexes pentanuclear carbonyl anions, 1815, of cyclooctatetraene, 24155-156 211-212,233-234 pentamethylcyclopentadienyls, molecular rearrangement of isocyanide 24160-161 cluster, 16332 Neophyl radical, rearrangement, M74 organometallic chemistry, 829-83 Neptunium, tetrahydroborate, 2k63 reaction with benzyl bromide, 38:73 Neutron bombardment, of bisbenzene- tetracarbonyl, 1316-17 molybdenum, 1391 in phase-transfer-catalyzed allylhalide Neutron capture, and nuclear transforma- carbonylation, 19:197 tions, 11:209 in triosmium clusters, 26:78-79 Neutron diffraction studies, on bisarene triple-decker cyclopentadienyl cation, complexes, 1351 18306-307,325,328 Nickel rJickel, q3 allyls addition reactions of zero-valent com- chiral phosphines, 19291-293 plexes chiral pinenyls, 19291-292 to metalcarbenes and metalcarbynes, cyclopentadienyl compounds, 19280, 282 18:231-232 isomeric bis-complexes, 19:279-280 Nickel 198

phosphine adducts of bis-compounds, cyclization, 12142-143 19283-286 linear oligomerization, 12143 Nickel, anionic ethylene complexes, 19:lOO- telomerization, 17:143 102, 106-107 codimerization of ethylene and butadi- alkyls, 19:100-101, 110-111 ene, 12291-308 hydride, 19101 1:2 adduct formation, 12291 phosphido-bridged, 19101 allyl intermediates, 12291-294, 298- Nickel, anionic hydride complexes 300 304-17:307 reactions, with Lewis acids, 2231 use of bis-cyclooctadiene complex, spectroscopic propcrties, 225-7 12295-298 structural properties, 2215-18 hydrogenation Nickelasilacyclobutene, 3988-89 by isocyanide cluster, 12370 Nickel carbonyl on support, 12365 with aryllithiums, 8:47 hydrosilation carboxylation reactions, 6157 asymmetric synthesis, 1R429 mass spectrum, 6275 via bis-cyclooctadiene complex, 12430 coupling of allylic halides, 840 of conjugated dienes, 12442 insertion reactions, 845-48 via Ziegler-type catalysts, 12430 reactions, with acetylene and carbon mon- olefin oligomerization, 12105-137 oxide, 841 dienes, 12125-128 synthesis, 82 dimerization, 12114-117, 128-135 Nickel carbonyl, acetylene complex, enantioselectivity control, 12134-137 2:26-27 formation of active species, 1214-119 anionic derivatives, 2249-250 preparation of catalyst, 12107-109 carbonylation by, 23-9 selectivity control, 12119-137 dative a-bonding, 2:10 structure of active species, 17:114-119 electronic structure of Ni-C bond, 29-10 reduction of CO to methane, 1262-63 kinetic liability, 210 Nickel complexes ligand exchange, mechanism, 211-12 acyclic pentadienyl, 26141-143, 154 reactions with alkynyl, 3887, 89 bis(acry1onitrile)-nickel, 213-1 5 allyl and carbon dioxide, 22161 cyclopentadiene, 212- 13 r-ally1 halide, cross coupling to alkyl ha- dicyano and tricyanoethylenes, 215-16 lide, 26202-209 duroquinone and cyclic olefins, 219-21 arene, 1366,117-120 duroquinone and trialkylphosphines, azobenzene, 1457 222 benzdiyne, synthesis and reactivity, quinones, 217-26 42177 substitution reactions, 29-12 benzyne Nickel carbonyl derivatives reactivity, 42172-173 CO exchange, 3250 synthesis, 42169-170 phosphine, 85 bimetallic, 32257-258, 283-284 phosphine complexes, 3:247-250 binary pentadienyl, 26135 Nickel carbonyl-phosphine complexes boranes, 2k63-66, 70, 77 cyclization of acetylenes, 227 clusters, 2k99-101 polymerization of alkynes, 229-30 borohydride, 13278 Nickel complex-catalyzed reactions t-butyl isocyanide, 11:70 but adiene carbene, 144 cocyclization, 12142 carbon dioxide, 22132 comparison with palladium, 12141-146 carbonyl cooligomerization, 12143 eigenvalue spectra, W196-197 199 Nickel

isoelectronic, 30:195-197 metallacyclopentanes, 24314-315 carbonylation, 1k137 polymer-supported catalysts, 15225-226 carbyne, coupling reactions, 2284 reactions with as catalysts for acetylene oligomerization, bis(trimethylsilyl)diazene, 23:185 15224-226 isocyanides, 1k29, 32 a-complexes. catalytic cyclization of redistribution reactions dienes, 238-45 alkyls, 23118-119 cyclohexyne, synthesis and reactivity, nickelocene, 23105-106 42190-191 nitrosyls, 23126 cyclopentadienyl phosphine halides, 23105-106, 117 nickelocene, 30216 silene, 3988-89 triple-decker sandwich, 30:217 sulfur dioxide insertion reactions, 12~68 1,4-diaza-1,3-butadienes tetracarbonyl, I3C NMR spectrum, U150 as butadiene oligomerization catalyst, trimethylenemethane 2k233 in organic synthesis, 22301, 306-307 with chelated ligands, 2k160-161, 169, synthesis, 22285 184, 189 trinuclear p-methylene, 20185 NMR studies, 2k209-210 vinylidenes, 2271, 94-95 disubstituted nickelocenes, 2k8 Nickel complexes, electron-transfer reac- face-bridged C,O-bonded carbonyls of tions Group I11 derivatives, 23260-264 p-alkynecyclopentadienyls, 24:llO hydrosilylation, 11:309-310 ally], 2337 iminooxosulfurane, W.185-186 aryl, 2335 isocyanides, 1k68-74 carbonyl, 23:33 IR spectra, 1k72 catalyzed C-C bond formation, 2335 oxidative addition reactions, 11:71-73 cyclopentadienyls, 23:62-63 ketene insertion and, 28:s nitrosyl, 2363 main group of duroquinone, 2341 germanium, tin, and lead, 3k127-128 fulvalenes, a95 tellurium, 3kl68-169, 173 hexanuclear cyclopentadienyl, 24:121 mass spectra, 8278-283 nickelocene, 2377 cyclopentadienyl derivatives, 8278-280 phosphines, 2333 olefin, 8280-281 reductive elimination, 2334 via metal atom synthesis, 1559-60, 99, thiolate-bridged dimers, 24110 101 trinuclear cyclopentadienyls, 24:120-121 insertion reactions, 15101 triple-decker sandwich, M95-96 naphthalyne, synthesis and reactivity, Nickel complexes, organolithium deriva- 42180-181 tives nonrigid cyclooctatetraene, 16:340 cyclododecatriene, 24:400-401 1,2,5,6-~*-octafluorocycloocta-l,3,5,7- dinitrogen, 24:405-409 tetraene, 3k241-242 norbornene, M400 olefin, with organolithium reagents, , W.404, 406 19~99-104, 108-1 11 trinuclear derivative, 24~402 perfluorobicyclo[3.3.0] octadienyl, Nickel, dilithium olefin complexes 3k242-245 bis(cyclooctadiene), 19108 phenylethynyl, 38128, 135, 137 cyclododecatriene, 19108 phosphine, 854-59 in ethyllithium synthesis, 19110-111 as Ziegler-Natta catalysts, 18130 olefin displacement, 19:108-109 photochemistry reaction with hydrogen, 19110 cyclopentadienylalkyls, 24312-314 in synthesis of Li[AIHEt,], 19110-111 Nickel 200

X-ray structural studies, 19109 [N~,(CO),,(ASP~)~]*~,structure and bonding Nickel, dinitrogen complexes, 19104-108 factors, 4234-35 and ammonia formation, 19:107 [Ni(cod)( q2-S=C(CF,),}], synthesis, 43147 mechanism of formation, 19:104-107 Ni8(C0)12(PCMe3)2(PMe),,structure and nitrogen displacement, 19106-107 bonding factors, 42:31 preparation, 19104 NiY(CO)l((PPh)h,synthesis, 4278 side on bonding, 19104-108 Nix(C0)4(PPh3)4(PPh)6,synthesis, 4281 X-ray structural studies, 19104-106 nido-Carboranes, 3612 Nickel-graphite, 28: 12 1- 122 compounds Nickel isocyanides, 22237-238, 249. 261 2-vertex, 36:39-40 electrochemistry, 22256-257 4-vertex, 3633-34 homoleptic species, 22223 hertex, 3634 tetranuclear cluster, 22214, 223, 249-250 6-vertex, 3632-33 alkyne reactions, 22254-255, 266-267 7-vertex, 36:34-35 fluxionality, 22242-243 8-vertex, 3634-35 Nickel, 13C NMR spectra 9-vertex, 3634-35 alkyls and 'JcH,19264-266 10-vertex, 3635-36 cyclododecatriene complexes, 19269, 11-vertex, 3636 271 -274 12-vertex, 3636-39 1,s cyclooctadicne complexes, 19272, 275 electron counting, 36:3 1 and equilibrium constants for olefin coor- geometrical systematics and electron pair dination, 19267-268 relationships, X22-25, 27-29 $-cyclooctenylphosphinc complexes, Lewis base adducts, 3630 19289-290, 294 structures, 3616-17 metallacyclopentanes, 19300-301 Nineteen-electron organometallic radicals, methyl bridged allyl, 19265 see also Cobaltocene phosphine olefin complexes, 19269-270 acidity, a177 relaxation times for $-cycIooctenyIs, electron distribution, 40:178 19262-263 interconversion with seventeen-electron and structure of v3,73-dodecatriendiyl radicals, 40:179-182 complex, 19:286-287 ligand binding, 40:179 tris(olefin)complexcs, 19268-270 migratory insertion Nickelocene alkyl to acyl migration, 40204 structure and reactivity, 5119 equilibrium constant for carbonyl inser- substitution reactions, 10:392-393, tion, 40:203 401 -406 hydride migration, a204 acetylenes, 10405 photolysis intermediates, 40179-180 azobenzene, 10403-404 reactivity iron carbonyl, 10405 comparison to eighteen-electron radi Nickel platinum clusters cals, 40171 high nuclearity ligand substitution and atom ab- cherry crystallite, 31:374 straction hydride, interstitial site, 3k375-376 cyclic voltammetry, 40.196, 199-201 octahedral core, 3k374 electrocatalytic substitution, 40:194- physicochemical property, 3k374-375 195,202 molybdenum species, 3k381-382 indcnyl effects, 40199-200, 203 tungsten species, 31:380 kinetic studies, 40:196-197, 199-201 NixC14(PPh)3(PPh)6,structure and bonding mechanism of ligand substitution, factors, 42:32 40:196 201 Nitriles

molecular orbital analysis, insertion into metal-carbon bonds, 40:202-203 U:72-73 phosphorus donors, 40:201-202 metal carbonyl complexes, 821-22 reductive activation, 40:193-196 reaction with B2Q,10263 redox-induced isomerizations, 40.205-207 Nitric oxide complexes, via metal atom syn- redox switches, 40:207-209 thesis, 1564-65 synthesis, 40:181-183 Nitrido clusters, 2462-82 types, 40177 carbonyl substitution, 2462 Niobium comparison with carbido clusters, 2469, carbenes, 37:272 73-74 carbonyls, 2182 bonding, 2473 metallacycles, 26:100 carbonylation reactions, 2474 mixed alkali metal compounds, 27:212, coordination numbers, 24.73-74 251 fluxionality, 2476 penta-alkyls, 14207, 237-238 NMR spectra, M74-76 pentacarbonylmetallate anion, see Penta- comparison with metal nitrides, 2482 carbonylmetallate(3-) of niobium dynamic properties, W.76-77 and tantalum of butterfly structure, 2476 Niobium complexes carbonyl migration, 2476 acetylene, 1056 effect of hydrogen-bridging, 24:77 anionic hydride, spectroscopic properties, isomerization mechanism, 2477 27:4,6,24-25 isocyanate formation, 2480-81 arene, 1360-61, 105 moderation of nitrogen reactivity, 2473 N-H bond formation, M78-79 bisarene, via metal atom synthesis, 1589 “N NMR spectra, U63, 74-76,78 bis(cyclopentadieny1)ethyl hydride, migra anomalous chemical shifts, 24:74, 76 tory insertion reaction, 26189 of butterfly structure, 24:75 II-C,O-bonded cluster, 23275-276 effect of metal series, 24:75 borane, 21:64, 85, 87, 91 effect of protonation, 2475 carbon dioxide, 22:132 protonation carbonyl diazene, 3493 at metals, 2475-76, 79 electron-transfer reactions at nitrogen, 2478-80 cyclopentadienyl alkyls, 2346, 78 structures, 2469-72 fulvalene derivatives, 24:95, 100 synthesis, M62-69 hydride-bridged cyclopentadienyl, from azide ion, 24:67 2499 via cluster interconversion, 24:68 seven-coordinate carbonyls, 235 via coordinated cyanate, 24:67 metal carbonyl adducts, 23272-273 from nitrite ion, 2465 photochemistry, bis(cyc1opentadienyl)al- from nitrosonium ion, 24:62, 64-65 kyls, 24:272-274 via nitrosyls, 2456-57, 65-67 silylmethyl, 1k316 Nitrile cleavage reactions, in synthesis of Ni(0) compounds, synthesis with C8K, tungsten alkoxides, 27:323 28106-107 Nitrile oxides, reactions NiR(PPhJ4(PPh),, synthesis, 42121 with germenes, 39300-301 [N~(P~Bu~)~]P,~,structure and bonding fac- with tin doubly bonded compounds, tors, 42:74 39316-317 Nitration, triphenylbenzene, 44:39-40 Nitriles Nitrato derivatives, 10182 alkylation, 28:99-100 Nitrene complexes, 10129, 136 metal carbonyl complexes, 10141 Nitric oxide n-bonded, 10147 Nitriles 202

stability and bonding, 10142-143 2-phenylpyridine, 34.39 syntheses, 10148-149 planar, 3449 synthesis, 11:171 planar tridentate, 3442 Nitro aldolizations, promoted by alkali polydentate, 342, 21, 42,49 metal, 28.101 poly(pyrazo1-1-yl)(pz), M2-55 Nitroarenes, reduction reactions, 28203 pyridine, 341, 20, 39, 48 Nitro derivatives, 10:183 pyridin-2-yl(py), 342, 21-22, 33, 35, 43, Nitrogen 46 elimination from a-diazophosphines, tetradentate, M42 44.180-181 tripodal, 3449, 52, 55 heterocarborane, 30:144-146 unidentate, 34:45 structure, 30146 Nitrogen fixation ionization potential, 30198 arene complexes in studies of, 1351 tcrphenyl derivatives, 44:39-41 by titanium compounds, 9185-188 Nitrogenase enzyme, 2203 Nitrogen hydrides, 23131-1 33 Nitrogen-bridged iron carbonyls, silyl derivatives, 23133 10119-120 Nitrogen oxide, for preparation of organo- Nitrogen-centered radical, reactions metallic 0x0 compounds, 28343-345 with Si hydrides, &81 Nitrogen-substituted carbene complexes with Sn hydrides, M102 reactivity Nitrogen donor complexes of metal carbon- carbene ligand rearrangement, 25155 yls, 10115-186 ligand substitution reactions, 25154 amino, 10117 nucleophilic substitution reactions at aminoborylcne, 10:167 Ca, 29149-154 aminocarbene, 10165 oxidative addition reactions, azido, 10129 25154-155 azo compounds, 10131 spectroscopic properties, 25149 carbamoyl, 10:122 structure, 29146-148 dialkylcyanamide, 10:151 synthesis, 25135-146 diazo, 10125 Nitrogen transition metal complexes heterocycles, a-bonded, 10138-141 in biological systems, 2203 kctenimine, 10:158 cobalt complexes, reactions, 267 methyleneamine compounds, 10160 iridium complexes, 265-66 ortho-metallated, 10157 formation from azides, 284 nitrene, 10129 titanium and zirconium complexes, 2166 nitriles, 10:141-151 Nitrogen ylides, 14:207-209 nitroso, 10153 reactions, 14207 phosphorimide, 10:164 synthesis, 14:207 Schiff base complexes, 10154 Nitrones, reaction with germenes, o-semidine, 10:136 39:300-301 ureylene, 10121 Nitrosation, of organocobalt compounds, Nitrogen donor ligands, 342-38 1k425 2-benzylpyridine, M39 Nitroso compounds, 11:170 bidentate, 341, 6-7, 21, 38 Nitrosyl clusters, 2441-67, 70 2,2'-bipyridyl, 341, 6, 34, 38, 42-43, 46 bonding, 2449, 55 intramolecular coordination systems, IR spectra, 2450-51,54-55 347,ll-12 and isotopic substitution, M55 metallated, 3448 metal-centered reactions, 24:61-62 N-methylimidazol-2-yI(mim),342, 21-23, carbonyl substitution, 2461 34, 50 kinetics and mechanism, 246-62 203 NMR

nitride formation, 2456-57 acyclic, A%-silicates, 44.226-227 ISN NMR spectra, 2450-51, 55-56 alkenyl-metal compounds, 337-41 chemical shift vs. nitrosyl bonding, alkyldiboranes, 3289-290 2455 alkyl-metal compounds, 321-25 0-methylation, M57 a-ally1 complexes, 371-91 0-protonation, 24:57-59 amino (1-alkynyl) carbenes, 4k169 acid dependence, 2458 2-amino-l-metalla-l-en-3-ynes, isomerization, 24.58 4k195-197 reduction of NO, 2459 arene complexes, 3150, 153-154 with hydrogen, 2459-60 azulene complexes, 3107-113 structures, M49, 52-54 li-bonded organometallic compounds, synthesis, M42-49 347- 156 condensation of nitrosyl fragments, cr-bonded organometallic compounds, 2447-49 34-47 from nitric oxide, 2442-43 boranes, 3289, 294, 297, 303 from nitrite ion, M45-47 butadiene complexes, 392, 103 from nitrosonium ion, M43-45 I3C, germenes, 44:119-120 Nitrosyl complex catalysts carbocyclic olefin-metal compounds, in hydrogenation, 17:332-333 3:53-62 ruthenium carbonyl cluster, 12371 carboranes, 3336-337 molybdenum in olefin metathesis, 12453 cobalt-alkyne complexes, 4k82, 84, 95-96 Nitrosyl complexes, 8223,225-226, 235 cyclobutadiene complexes, 4118 and associative substitution, 2k123-124 cycloheptadiene complexes, 399 cobalt, 3240-241 cycloheptatriene complexes, 399 electron-transfer reactions, 2311, 2101- cyclohexadiene complexes, 397-98 104, 106, 122 cyclohexadienyl complexes, 3129-132, cobalt, 2332-33 149 iron, 2328, 37 cyclooctatetraene complexes, 399-100, isomerization, 2316 106, 161 manganese, 2352 cyclooctatriene complexes, 3100, 156 tungsten, 2349 cyclopentadiene complexes, 3:94-96 iron, 3229-230 cyclopentadienyl complexes, 3114-127 manganese, 3215-216,219, 222 determination of magnetic susceptibility, in olefin metathesis, 16284 34 double cross experiments, 16286-287 diboranes, 3289-290 redistribution reactions, 23126 diene complexes, 3105 vanadium, 3196 diolefin complexes, 354-63 Nitrosyl metal carbonyls, 2216-222 ethyl-metal compounds, 316-21 Nitrosyl metal complexes, organometallic, exchange of bridging and terminal 2211-236 groups, 8194-196 with alkyl or ally1 groups, 2229 fast exchange reactions, 8167-205 bonding, 2212 8-ollyl complexes, 8:106 preparation, 2216 organo-Group I11 derivatives, spectral properties, 2231-235 8193-196 structures, 2213 exchange studies, 3156-159 Nitrosyl metal cyanides, 2222-224 ferrocenes, 3114, 127-129, 135-149 Nitrosyl metal isocyanides, 2222 fluorocarbon derivatives, 326-29,31, 35, Nitroxides, as spin traps for pentacyanoco- 43-47 balt(I1) salts, 15313 Group IV organosulfur derivatives, NMR 541-42 NMR 204

heteroaldehyde and heteroketone transi- acylmetalloids, 2117 tion metal complexes. 43135-136 d4 alkyne complexes, 2944-61 main group-transition metal clusters, determination of stereochemistry of phos- 42127- 128 phine complexes, 7:59-60 methyl-metal compounds, 35-16 heteronuclear clusters, 29302-303 munocyclic A5Si-silicates with Si02FC2 ,!l-ketornetalloids, 7:149 skeleton, M266, 268-269 metal nitrosyl complexes, 2234 a-olefin complexes, 347-156 silicon-transition metal compounds, C2 system, 347-71 11:286 C3 system, 371-91 thallium complexes, 1k165 C4 system, 391-113 transition metal alkyls(aryls), R168-170 C5 system, 3114-154 "B NMR spectra C6 system, 3150-155 metalloboranes, 2k82-84, 89, 91-92, C7 system, 3155-156 102-103 organoarsenic compounds, 4222-223 chemical shifts and bonding, 2k83-84 organolithium compounds, 3381-383 comparison with boranes, 21:83-84 phenyl-metal compounds, 341-43 nonahydrotetraborate anion, 21:79 phosphinocarbenes, 44.184-185 "C NMR spectra polygermanes, 444-45 assignment of L3Cresonance, l2:136-137 polysilanes, 4:28-29 broadening by cobalt and manganese, polystannanes, 458 12138 RuSC(CO) 15, 4346 carbidocarbonyl clusters, 22:46-48 Ru,C(C0)17, 43~46 and carbonyl substitution mechanisms, 77Se,44:161-162 2k132 silyene complexes, bridged, 42272-273 of complexed phosphorus donors, silyene-Lewis base complexes, 4313, 37 1R294-301 spirocyclic A'S-silicates coupling constants, fi15.5-165 with SiO4C skeleton, 44233-234 dicyclopentadienyl Group IV com- with acetohydroximato(2-) bidentate pounds, 19133 ligand, 44.255-256 diene complexes, 2413-15 with benzohydroximato(2-) biden- experimental techniques, 12136-140 tate ligand, 44:255-256 off-center double resonance, with ethane-1,2-diolato(2-) bidentate l2136-137 ligand, 44:240 formyl complexes, 2013 with ethene-1,2-diolato(2-) bidentate isocyanide complexes, 22238-243 ligand, 44:238-239 nitrido carbonyl clusters, 2476 with a-hydroxycarboxylic acids, organometallic compounds, 2135-206 W.247, 249-251 organo-transition-metal complexes, with salicylato(2-) bidentate iigand, 19257-304 a254 chemicals shifts, 19:260 with SiOrNzC skeleton, M258-259 coupling constants, 19260 with SiO&C skeleton, 44:261 relaxation times, 19:261-263 with SiOr skeleton, M263-264 a-methylene Complexes, 2&209-215 lzSTe,44.161-162 pro3adienylidene complexes, 22110 time-dependent phenomena, 3156-161 signal-to-noise ratios, fi138 tropyne-transition metal complexes, variable temperature, l2146-150 42185-186 Group IVB cyclopentadienyls, valence tautomerism, 3159-161 2147-148 vinyl-metal compounds, 332-35 mercury cyclopentadienyls, 12147 NMR spectra vinylidene complexes, 2297, 104, 107 205 NMR spectroscopy

ylide complexes, 20131 ketenylidene complexes, 2&68 protonation, 20131 ligand dynamics, 32100-107 structure, 20126-128 magnetization transfer measurements, 19FNMR spectra B445-446 and five-coordination at silicon, using decoupling, 28446-448 20~274-275 using selective pulses, 28448-450 and fluorophenylgold complexes, 2045 manganese- and rheniumpentacarbonyl al- 'H NMR spectra kyls, 3R180-181 formyl complexes, 2013 multinuclear, B442-445 and organosilane stereochemistry, nucleophile-carbonyl complexes, 20273-274 B151-155 a-methylene complexes, 20209-214 one-dimensional sulfur dioxide insertion products, 12:34 decoupling difference, 28400-404 tetrazenes, 24209, 211 heteronuclear experiments, 28408-424 and isomerization, 24215 nuclear overhauser enhancement differ- triazenes, 24:191, 193, 196-198 ence spectroscopy, 28404-408 ylide complexes, 20:128, 131 resolution enhancement, 28:398-400 ''N NMR spectra organoberyllium compounds, 9217-219, nitride clusters, 2463, 74-76, 78 246 nitrosyl clusters, 2450-51, 55-56 organopolysilanes, 685-88 "0 NMR spectra, and carbonyl substitu- 31P,phosphasilenes, 39204-205 tion mechanisms, 2M32 phosphinemethylenes, 9297 31PNMR spectra, hydroplatinum phosphine proton exchange, 9293-295 complexes, 13342 polystannanes, 38:202-203, 212-214, 216- 1 I9Sn NMR spectra, organotin(I1) com- 217, 227-228, 238 pounds, 19133 recent developments, 28397-398 NMR spectroscopy in redistribution equilibria studies, agostic C-H groups, detection, 28320 6~186-193 agostic neopentyls, 28320-322 interpretation, 6187 alkynyl-metal complexes, 3881, 89 and redistribution reactions, 23101-102 allenyl compounds, 3293-100 relationship between Sn-H and Sn-C-H, anionic transition metal hydrides, coupling constants and Mossbauer 2x2222-24 isomer shifts, 958 a-arene-a-cyclopentadienyliron cations, relaxation measurements, Zk450-451 10:85 silenes, 3995-97 arsasilenes, 39225 silyl anions, 387-9, 26-27, 48-49 "B, borabenzene metal complexes, solid-state 25207-209 room temperature, 28451-455 cobalticinium salts, 1088 variable-temperature, 28.455 cymantrenes, 1089 system MeGeClz/MeGeO, 6200 dihydrogen complexes, 28303, 306 system MeGeCI3/MeSiBr3, 6188 disilenes, stable, 39242-243 system MePClz/MePBrz, 6199 ferrocenes, 1082 system MeSiClz/[MezSiNMel3,6190 chemical shifts, 1083-84 tin double bonded compounds, heteroannular substitution, 10102 39306-308 Gaussian enhancement of, 283399-400 titanocene derivatives, 10:104 germanium doubly bonded compounds, trimethylaluminum, temperature depen- 39283-284 dence, 6215 ketene complexes, B32-34 trimethylenemethane osmium complexes, ketenyl complexes, 2855-56 22292 NMR spectroscopy 206

trimethylplatinum(1V) compounds, phosphasilenes, 39:204-206 21132 silenes, 39:9S-97 tungsten alkoxides, 22314 NMR studies two-dimensional, 28:424-426 on ally1 complexes, 16249-250 hetcroscalar correlated, COLOC. fluorocarbon metal compounds, 28440-441 k206-212 heteroscalar correlated. heteronuclear of stereochemical nonrigidity, 16211-222 correlation using 'J(X,'H), ' 'B NMR studies, complexes of boron het- 28435440 erocycles, 18307-337 homoscalar correlated, 28428-430 "C NMR studics INADEQUATE, 28430-431 arsenic ylides, 14226 J-resolved heteronuclear, 28432-43s of butadiene polymerization by com- J-resolved homonuclear, 28426-428 plexed n-butyllithium catalysts, nuclear overhauser effect, 28431-432 1867-71 RELAY, 28:441 degree of polymerization, 1867-68 wide-line studies of organosilicon com- mechanism, 1875-77 pounds, 912-15 carbene complexes, 14:14 "C NMR spectroscopy carbyne complexes, 1425 carbync complcxcs of 0s and Ru, 25188 chemical shifts in ethylene con~plexes, C.0-bonded carbonyls, 23:225, 246-247 1518 alkylated compounds, 23250-251 on cyclopentadienyl iron dicarbonyl di- end-on bonding, 23223 mer, 16319-320 II-bonding, 23224 of dinuclear olefin complexes, 16336-338 halocarbene complexes of 0s and Ru, dynamic properties of mixed-metal clus- 25: 175 ters, 18:208, 257-264 N-, 0-,S-, or Se-substituted carbene com- high nuclearity metal carbonyl clusters, plexes, 25149 14308-310 nonheteroatom-substituted Os, Ir, and chemical shift and charge on CO, Ru carbene (alkylidene) complexes, 14309 25163 fluxional behavior and reactivity, silenes, 3997 14309-310 and *'Si NMR, chemical shifts for silenes, homogeneous dicyclopentadienyltitanium 2514-15 Ziegler-Natta catalysts, 18129-1 30 'H NMR spectroscopy nonacarbonyltricobaltcarbon carbonium borabcnzene metal complexes, ions, 14130-134 23207-209 penta-alkylphosphoranes, 14216 Group 4B metallocene dicarbonyls, phosphorus ylides, 14212-213 25348-350 on polynuclear carbonyls nonheteroatom-substituted Os, Ir, and iron, 16326 Ru carbene(alky1idene) complexes, mixed metal hydride, 16334 25163 osmium anion, 16335 oligocarbene Ru(I1) complexes, 25149 ruthenium hydride, 16:333 Ru, 0s. and Ir secondary carbene com- of thermal rearrangement of bis(trimeth- plexes, 25149 ylsilyl) ester, 1658-60 "Si NMR spectroscopy, 23193-194 on titanium dinitrogen complexes, 16273 arsasilenes, 39221 'H NMR studies DEPT and INEPT techniques, alkylaluminum halide cocatalysts, 23195-208 11303-304 disilenes, stable, 39:242 arenemetal tricarbonyls, 1356, 87 limitations, 23193-194 arsenic ylides, 14226 207 Nonacarbonyltricobaltcarbon-substituted carbonium ions

methyltin halide complexes, 1477, 79-81, chromium carbonyl complexes 83-4, 86-91 physical properties, 3480-90 methyltin halides, 1465-66, 69, 71-72, reactivity, 3490-93 75-76 synthesis, 3480-90 dependence of J('I9Sn--C--'H) on sol- coordination, modes of, 3k70-72 vent, 1465-66 diazenes, electronic structure, 3469-70 nonacarbonyltricobaltcarbon carbonium 1,3-dienes, reactions with ions, 14130-134 2,3-l-diazaferroles, photo-Diels Alder olefin complexes, 14:44 reactions, 34103-104 organoantimony compounds, 14189-191 1,2,3-diazepinones, iron assisted synthe- organometallic heterocycles sis of, M98-103 with delocalized a-electron systems, general synthesis, M70-72 13252-260 iron carbonyl complexes solution structures, 13229 physical properties, 34:72-79 penta-alkylphosphoranes, 14216 reactivity, M79-80 phosphorus ylides, 14212 synthesis, 3472-79 of u-n rearrangement in platinum molybdenum carbonyl complexes ethenol complex, 16250-252 N - N bond on silylhydrazide anions, 16:7-13 complexes formed by cleavage of, 'H NMR studies, chiral metal complexes 3493-98 analysis of diastereoisomeric enantiomer complexes formed with retention of, mixtures, 18191 3472-93 determination of optical purity, physical properties, 3480-90 18166-168 reactivity, 3490-93 square-pyramidal molybdenum and tung- rhodium carbonyl complexes synthesis, sten complexes 3489 inversion of configuration, 18:180 synthesis, 34230-90 rate of epimerization, 18178-179 ruthenium carbonyl complexes 'H NMR studies, hydroplatinum complexes physical properties, 3478-79 containing amibidentate ligands, reactivity, 3479-80 13341-342 synthesis, 3478-79 correlation between Jpf H and Hammett summary, 34:104-105 up-parameters, 13338-340 tungsten carbonyl complexes correlation between JP,.H and "pt-H, physical properties, 3480-90 13338-340 reactivity, 3490-93 JP.H data, 13343-353 synthesis, M80-90 JP,-H data, 13345-353 Noble gas rule, and high nuclearity metal second order effects, 13340-341 carbonyl clusters, 14336-338 structural studies, 13292-293 Nonacarbonyltricobaltcarbon compounds, t values for hydride resonances, radical anions, l5313 13343-353 Nonacarbonyltricobaltcarbon-substituted 31PNMR studies carbonium ions, 14119-134 penta-alkylphosphoranes, 14216 consequences of charge distributions, phosphorus ylides, 14212 14123-128 N-N group, organometallic chemistry fluxional behavior, 14134 alkynes, reactions with, 3498-104 u-a hyperconjugation, 14133 2,3-l-diazaferroles, photo-Diels Alder NMR spectra, 14129-134 reactions, 34103-104 reactions at carbon, 14122-124 1,2,3-diazepinones, iron assisted synthe- structure, 14129-134 sis of, 3498-103 synthesis Nonacarbonyltricobaltcarbon-substituted carbonium ions 208

from alcohols and HPFh,14122 equation, 42297 via protonation of vinyl derivatives, response 14: 125 inorganic salts, 42292 as weak electrophiles. 14122-123 organic compounds, 42292-293 Nonahydrotetraborate anion, 21:79-80 organometallic complexes, 42:293-294 and butadiene analogy, 2k7Y speed of processes, 43350 I'B NMR spectra, 21:79 systems of units, 42298-300 structure, 2k76 third-order nonlinearity, see Third-order Nonamethylcyclopentasilanyl-potassium, optical nonlinearity 3833 Nonmetal hydrides, in oxidative-addition re- Nonaphenyltetrasilanyllithim, 3832 actions, 270 Nonasilane, 3832 Norbornadiene Nonclassical ions, 11:9 manganesepentacarbonyl alkyl reaction, Nonconjugated diene-Fe(CO)? complexes, 32200 1~8-9,11, 18-20 nickel-catalyzed dimerization, 17:199, 204 Nonlinear optics reaction with silenes, 39120 absorption loss, 43350-351 Norbornadiene complexes applications, 42291, 43349-350 of rhodium and iridium, from cyclohepta- computational methodology, 42309-315, triene, 4363 348,352-354 solvolysis, 10364 displacement vector, 42300 Norbornene, reactions with metal atoms, electric field vectors, 42294-295, 299 1561-62 macroscopic theory, 42297-298 Norbornyl cations, 11:lO measurement of organometallic second- Norbornylene, manganesepentacarbonyl al- order nonlinear opticaI properties kyl reaction, 32200 bulk measurement, 42315, 318-319, Norcaraneiron complex, sulfur dioxide inser- 321, 324 tion reaction, 12:58 comparison between results, NQR, n-ollyl complexes, 8106 42308-309 "CI NQR spectra, gold complexes, 2058, hyper-Rayleigh scattering, 42306-308 99 Kurtz powder technique ,42301-303, NQR studies 315, 318-319, 321, 324 aluminum alkyls, 15241 molecular measurement, 42324-325. methyltin halides, 1466, 72 328, 330-331,336-338, 344, 346, molecular complexes, 1479, 81, 83, 87, 348 89-91 second harmonic generation mea- Nuclear magnetic resonance, see NMR surement Nuclear Overhauser effect, 16:222 crystals and films, 42303-304 and high field I3C NMR spectra, clcctric-field-induced technique, 19259-261 42304-305 removal by paramagnetic compounds, solvochromism, 42303 12138 nonlinear optical coefficients, calculation, Nuclear Overhauser effect NMR spec- 42312-313 troscopy organometallic compound features, over- one-dimensional, 28404-408 view, 43351 two-dimensional, 28431-432 organometallics in applications, 42356 Nuclear quadrupole resonance, see NQR Pockels effect, 42:296, 298 Nuclear transformations, chemical effects, polarizability variables, 42295-297 11~208-220 polarization Nucleophile-carbonyl adducts dimensions, 42299 alkoxycarbony 1 209 Nucleophilic addition

characterization of complexes, structural properties, 28:150-152 28155-157 synthesis procedures, 28141-150 decarboxylation of, 28184 water-gas shift catalysis and related reac- spectroscopic data, 28:151-155 tions, 28198-205 structural data, 28150-152 Nucleophiles synthesis of, 28:149 abstraction reactions, computer represen- carbamoyl tation, %192 characterization of complexes, addition reactions, computer representa- 28155-157 tion, 26:192 decomposition of, 28186 C-containing, reactions of dihalo- and formation, rate law for, 28170 monohalocarbene complexes of Ir, structural data, 28150-152 Os, and Ru with, 25179-180 synthesis of, 28149-150 N-containing, reactions of dihalo- and equilibria and kinetics of formation monohalocarbene complexes of Ir, reaction dynamics investigations, Os, and Ru with, 25178 28166- 170 0-,S-, Se-, and Te-containing, reactions thermodynamic and theoretical studies, of dihalo- and monohalocarbene 28960- 166 complexes of Ir, Os, and Ru with, examples by method of preparation, 25176-178 28~142-146 order of reactivity toward p-complexes, halocarbonyls, spectroscopic data, a153 W:50 homogeneous catalysis of water-gas shift reactions with reaction carbene or carbyne, 26:192 in acidic solution, 28196-197 carbonyl group, 26192 in alkaline solution, 28:187-194 dihydridodecacarbonyltriosmium, in aqueous organic amine solution, 26~50-52, 71 28194- 195 ~5-pentadienyltricarbonylironcations, carbonylations and, 28:203-205 2fk146-147 hydroformylations and, 28:198-201 isocyanide complexes, 1k36-42 hydrogenations and related reductions, transition metal carbynes, 2269-77 28:201-203 trimethylenemethane metal complexes, in neutral solution, 28196-197 22295-297 hydroxycarbonyl substitution reactions characterization of complexes, of arenemetal complexes, 1386, 98-99 28155-159 computer representation, -194 decarboxylation of, 28181-182 Nucleophilic addition spectroscopic data, 28:151-155 borabenzene metal complexes, structural data, 28150-152 23227-228 names and formulas, 28:140-141 carbene complexes, 25126-127 preparation and properties of, carbyne complexes, 25131-133 28:140-159 cationic arene complexes, 1350, 60 reactivities, 28:171-172 coordinated isocyanide and vinylidene li- with alkenes, a178 gands, 25138-140 decarboxylations and related processes, reactions of 0s and Ru carbyne com- 28179- 187 plexes with, 25192-193 hydrogenations, 28175-177 substitutions reductive eliminations, 28:178-179 at boron in borabenzene metal com- substitution, 28172-175 plexes with, 23228-229 role of, 28:139-140 nonheteroatom substituted Os, Ir, and spectroscopic properties, 28151-155 Ru carbene(a1kylidene) complexes Nucleophilic addition 21 0

halomethyl ligands as methylene pre- hydrocarbon analogue, 3k235 cursors, 25:167 Octafluorocycloocta-l,3,5,7-tetraenecom- to Os(=CH2)CI(NO)PPhi)2, plex, pcntamethylcyclopentadienyl co- 29167-168 balt and rhodium reactions at Ca of N-, 0-,S- and Se- formation of Substituted carbene complexes, cyclopentadienyl comparison, 25149-153 3k231-232 Nucleophilic behavior indenyl comparison, 3k232-233 of coordinated ketene ligands, 2849-51 mechanism, 31:231 of ketenylidene complexes, 28:74-75 perfluorobicyclo[3.3.O]octadienyl, Nucleophilicities, transition metal complcx 3k230-233 anions, ?161 pyramidalization, 3k233 Nucleophilic ring opening, of oxiranes, stable perfluorocyclooctatrienediyl, U:288 31: 22 9 - 2 3 0 g-7’ transformation, 3k229-230 trimethylphosphine ligand, 3k229 0 structure, 3k230-231 Octa-terf-butyloctagermacubane, 37:14 t-butylisocyanide ligand, 31:230 Octabutyltristannane, 38205 Octafluorocycloocta-l,3,5,7-tetraenederiva- Octa(t-butyl) tristannane. 38:207 tive cobalt complex Octacarbonyl-p-7’ ‘-1,3,5-cycloheptatrien-l- cyclopen tadienyl yl-p-h ydridodirhenium structure, 3k221 isomerism, a367 synthesis, 3k222 structure, 26368 transannular ring closure, 3k222 Octacarbonyl-p-7’ ’-tetramethyleneethane- electrochemical comparative study, dimanganese 31~226-228 structure, 26:362 cyclic voltammetry, 31:227 synthesis, 26359 cycloocta-1,3,5,7-tetraene,3k226-227 Octadicarbonyldicobalt reduction, 3k227 alkyne displacement, 4k71 ESR study, 3k227-228 cobalt-alkyne complex synthesis, pentamethylcyclopentadienyl, 3k225-233 4k70-71 electrochemistry, 31:226-228 Octadienes, via telomerization of butadi- isomer, 3k225-226 cnc, 17:151-168 synthesis, 3k225 Octafluorocycloocta-l,3,5,7-tetraene,bridg- radical anion ing indenyl rhodium complex cyclic voltammetry, 31:227 intermediate structure, 3k236-239 preparation, 3k226-227 cis coordination of two rhodium, relative rearrangement rate 3k236-238 hydrocarbon comparison, 3k228 mechanism of bridge formation, 3k238 isomerization slowing, 3k228 selectivc C-F bond activation Octafluorocycloocta-l,3,5,7-tetraenederiva- by chromatography, 3k239 tive nickel complex F-H exchange, 31:239 1,2,5,6-~2-octafluorocyclooctatetraene, stereochemical nonrigidity of bridging 3k241-242 ligand ligand effect on bonding mode, activation energy, 3k236 3k244-245 I9F NMR spectrum, 31:235-236 perfluorobicyclo[3.3.O]octadienediyl, mechanism interconversion, 3k235-236 31:242-245 synthesis and structure, 3k233-235 five coordinate species, 3k243 bonding, 3k233-235 mechanism, 3k244 21 1 Octahydrotetraborane

phosphine ligand dissociation, 3k244 synthesis and physical property of $-spe- phosphine reaction, 3k242 cies, 3k205-207 t-butylisocyanide preparation, 3k242 carbonyl replacement, 3k205 Octafluorocycloocta-l,3,5,7-tetraenederiva- hydrocarbon comparison, 3k2OS-207 tive palladium complex, perfluorobi- tricyclic route, 3k210 cyclo[3.3.O]octadienediyl, 31:241 Octafluorocycloocta-l,3,5,7-tetraene,and va- Octafluorocycloocta-l,3,5,7-tetraenederiva- lence isomer metallation tive platinum complex cyclooctatetraene, 3k245-247 perfluorobicyclo-[3.3.O]octadienediyl dimetallation, iron complex, 3k251-252 mechanism, 3k240-241 heptafluorobicyclo[4.2.0]octatrienyl, synthesis, 3k240 31~247-255 transannular ring closure, 3k244 7'-heptafluorocyclooctatetraenyl complex Octafluorocycloocta-l,3,5,7-tetraenederiva- chromatography, 3k251 tive rhodium complex chromatography, 3k251 cyclopentadienyl crystallographic study, iron, 3k248-250 bonding, 3k217-218 hydrocarbon comparison, 3k254-255 synthesis, 3k217 isodynamic process, 3k254-255 indenyl ligand substitution, 3k250-251 bonding, 32223 NMR dynamic study, 3k254 dynamic NMR study, 3k225 synthesis, 3k247-248 NMR study, 3k224 perfluorotricyclo[4.2.0.O]octa-3,7-diene slip-folding, 3k223-224 dimetallation, 3k252-253 structure, 3k223-224 structure, 3k252 synthesis, 31:218 synthesis, 3k252 pentamethylcyclopentadienyl Octafluorocycloocta-l,3,5,7-tetraene,vicinyl isomer, 3k225-226 defluorination, 3k255-260 synthesis, 3k225 cyclooctatneneyne structure, 3k255-256 perfluorobicyclo[4.2.0]octatriene dicobalt complex, 3k256-260 ring closure control, 3k221 bonding, 3k258-259 structure and bonding, 3k220 crystallographic study, 3k257-259 synthesis, 3k218-219 inversion barrier comparison, 3k260 valence isomer, 3k219 isodynamical process, 3k259-260 Octafluorocycloocta-l,3,5,7-tetraeneiron 31PNMR, 3k259 complex synthesis, 3k256-257 bonding mode, 3k212 Octagermacubane, 322, 17-19 hydrocarbon comparison, 3k211-212 Octahydrodiborate ligand, 2k86, 88-91 perfluorocyclooctadienyl formation, coordination modes, 21:86 3k215-217 cyclopropane analogy, 2k89 bonding, 3k217 fluxionality and complexation, 2k89-90 hard and soft nucleophile, 3k215-217 structural change on coordination, mechanism, of nucleophilic attack, 2k89 3k215 Octahydropentaborate anion, 2k75 synthesis, 3k211-212 Octahydrotetraborane, 2k76-79 X-ray structural study, 3k212-214 calculated structure, 2k77-78 Octafluorocycloocta-l,3,5,7-tetraenemanga- and cyclobutadiene analogy, 2k77 nese complex deprotonation, 2k82 $-hydrocarbon comparison iron tricarbonyl complex, 2k61, 77-79 dynamic NMR study, 3k209-210 MO calculations, 2k78-79 structural, 3k207-209 reaction with alkynes, 2k80-81 Octakis( fe~-butyldimethylsilyl)pentacyclo[4.2.O.O2.O3O4]-octasilane 212

Octakis(fert-butyldimethylsilyl) C6 system, 3150-155 pentacycl0[4.2.0.0~.0~0~]-octasi~ane, C, system, 3155-156 3215,22-23 Olefin dimerization Octakis(fert-butyl)octasilacubane, 3216-17 catalysis by supported metal complexes, Octakis(2,6-diethylphenyl)octagerma- 15224 cubane, 37:18-19.22 catalysts, 1942 Octakis(2,6-diethylphenyl)octasilacubane, by transition metal alkyls, 289, 199 3215, 21-23 Olefin hydrogenation Octakis(2,6-diethylphenyl)octastanacubane, catalyzed by 3219-20, 22 arenechromium tricarbonyls, 1386 Octakis(1-ethyl-1-methylpropyl) areneruthenium complexes, 13104 pentacycl0[4.2.0.0~5.01.R.04.~]0ctager- cyclopentadienyltitanium compounds, mane, 3218 1916-17,44-46 Octakis( 1,1,2-trimethylpropyl)octa- palladium and platinum complexes, silacubane, 3217 13331-336, 422 Octamethyldiarsaferrocene, 39330, 335, rhodacarbonane, 14183 339-340 transition metal alkyls, 2202 Octamethyl-1 ,1 ’-diheteroferrocene, 39330, mechanism, 13332-336 343-344 relative rates, 13331 Octamethyl1,l ‘-distibaferrocene, 39336 Olefin insertion reactions, theoretical analy- ($-Octamethylnaphthalene)( $-arene)Ru*+ sis of reaction pathway, 1511 complexes, 29168 Olefin isomerization, 7:201, 16260-263, Octanal, coupling with Ti-gr, 28:127 1941 of Octaphenylcyclotetrasilane, 37:7, 3832 ally1 alcohol, 16:262-263 via iron pentacarbonyl, 16262-263 Octasilacubane, 321-2, 14-17, 36 catalyzed by crystal structure, 3215 hydronickel complexes, 13311-313 precursor, 37:16 rhodacarborane, 14:183 theoretical studies, 322-4 supported metal Complexes, 15219, Octastannacubane, 3219-22 226, 228 1,3,7-Octatriene, via palladium-catalyzed bu- during hydroformylation, 1213-14 tadiene dimerization, 12145, 148-149 in hydroformylation reaction, 6124-128 Octa-l,3,6-trienes, 880-82 mechanism, 16260-263 Olefin cobalt IT complexes, 11:400 role of u-a rearrangement in catalyzed re- Olefin complexes, 126-15 action, 16:260-263 bonding, 12:6-12 Olefin metal complexes, I3C NMR spectra, “C NMR spectra, 12:153, 184 19267-278 formation from u-alkyl compounds, 2197 chemical shift correlations, 19267 iron carbonyl, 1:2 with C=C bond length, 19268 tetracarbonyl complex, k14 with n(C=C), 19268 mass spectra, 6291, 301-302 tetrahedral compounds, 19272-273 quinone nickel, structure, 224 trigonal planar compounds, 19268-272 substitution reactions, 10:355-365 a-Olefin metal complexes, cationic, 8121 platinum, 10356 mass spectra, 8231, 264-271, 276-277 rhodium, 10360, 362 Olefin metathesis a-Olefin complexes, NMR, 347-156 acyclic olefins, 12469-478 Cz system, k47-71 cyclic olefins, 12478-482 C3 system, 3:71-91 pentenes, 12453,461,479-481 C, system, 391-113 polymerization, 12451 Cs system, 3114-154 stereospecificity, 12478-479 21 3 Olefin polymerization

cyclooctene with 2-hexene, 16288-289 2-pentene, 16298 product composition, 16288-289 kinetics and mechanism, 16:298 cyclopropane formation, 12459-468 in pheromone synthesis, 12485 conversion to a-olefins, 12462-463 polarkation in carbene complexes, 12462 and metathesis termination, 12461 product composition in double cross ex- 2,8-decadiene, 12454 periments, 16284-288 formation of initial carbene complex, role of u-rr rearrangements in catalysis, 12451-459 16:269-271 via carbonyl insertion, 17:455 selectivity, 16299-305 hydrogen transfer processes, 12454, with 1-methylcyclobutene, 16302-303 456-459 with 1-methylcyclooctene,16:303-305 intermediacy of metal hydrides, 12455 with monosubstituted ethylenes, via organometallic cocatalysts, 16299-302 12453-455 with trisubstituted ethylenes, via stable metal carbenes, 17:451-453 16302-305 2-hexene, 16:306 self-metathesis of ethylene, 12457-458 highly strained cycloolefins, 17:453 stereochemistry, 12468-482 importance of olefin precoordination, acyclic olefins, 12469-478 12466 cis-[runs isomerization, 12468 lactone, 12487 cyclic olefins, 12478-482 via Lewis acid adducts of carbonyls, and cyclobutane conformation, 23241 17:473-478 mechanism, 16269-271,285-299, effects of alkyl substituents, 12470-471 12449-450 and olefin exchange process, double cross experiments, 16285-288, 295 12477-478 of pentene metathesis, 17:469-478 via metal carbene, 12449-450 , metal carbene chain, 16270-271, 290- stereospecificity 17:468-469 292, 295, 297 of triglycerides, 17:483-484 painvise vs. non-pairwise, 12449 of unsaturated esters, 17:483486 single cross experiments, 16288-292 stereochemistry of products, 16309-313 stereospecificity, 12450 from cis-1,2-disubstituted ethylenes, steric course, 12450 16309-310 sticky olefin hypothesis, 16:288, effects of Lewis acids, 16312-313 292-297 molybdenum vs. tungsten, 16:313 using metal carbene complexes, 16299- from truns-l,2-disubstituted ethylenes, 303, 305-308 16310 metathesis of acyclic olefins, from trisubstituted ethylenes, 16305-306 16:310-312 polymerization of cycloalkenes, and Tebbe’s reagent, 20196 16305-306 terminal olefins, 1e299-300 selectivity, 16305-306 selectivity of catalyst, 16:299-300 of tungsten carbonyl, 16300-302, yields, 16299 305-308 p-vinylidene intermediates, 20:186-187 and p-methylene complexes, 20193 Olefin polymerization, 2199, 16256-260 by nitrosyl complexes, 12453 organic halides as catalyst activators, norbornene derivatives, 17:486-487 12281 norbornene esters, 16308 by silylmethyl compounds, 11:322 olive oil, 12484 u-Brearrangements in catalyzed reac- civetone synthesis, 12484 tions, 16256-260 Olefin polymerization 21 4

by titanium-aluminum compounds, regioselectivity in dimerization, 9 182-185 12106-107 Ziegler-Natta process, 16256-260 selectivity control, 12105-137 Olefin polymerization, catalysis structure of active species, 12114-119 alkylidynetricobaltnonacarbon yls, Olefin transition metal complexes, 14137-138 16225-231 arenetitanium complexes, 1358 barrier to olefin rotation, 16:225-227 bisarenechromium complexes, 1369 effect of substituents, 16:226-227 organolithium reagents, 1855-97 bonding, 1434-37,1514-27 supported metal complexes, 15226-227 electron spectroscopy for chemical analy- Ziegler-Natta, 18:Y9- 149 sis, 1520 Olefins geometry, 1453-55 addition of boron-hydrogen bonds, five coordinate metal, 1455 1330-31 four coordinate metal, 1454 catalytic oxidation by 0x0 complexes, three coordinate metal, 1453-54 28:341-342 via metal atom synthesis, 1559 cocyclization with butadiene, 12142 molecular rearrangements, 16:336-341 cooligomerization with butadiene, dinuclear species, 16336-338 12179-180 trinuclear of olefin-metal bond, 16:226 1448-51 [l + 21 cycloadditions, 44:189-190 nonplanarity of bound olefin, 1524-27 electron rich carbene complex synthesis stability, 1437-55 from, 25140-141 structural studies, 1519-24 elimination from transition metal alkyls, structure, C=C 2186 effect of coordination on bond length, 1519 homologation, 201 95-196 effects of olefin substituents, 1519 hydroplumbation reactions, 2279-280 theoretical studies, 1514-27 hydrosilylation, transition-metal cata- Huckel calculations, 1520-21 lyzed, 11:297-310 twist of olefin, 1451-53 oxidation orientation of p-substituents, 1452 u-n rearrangements in catalyzed reac- pointing of trans-ligand, 1452-53 16:252-256 tions, variation of C=C bond length, 14:38-46 11:187 with thallium(II1) nitrate, correlation with chemical shift of ole- oxidative-addition reactions, 7:65 finic protons, 1444 oxythallation, 11:174-202 correlation with metal ionization poten- reactions with organoberyllium hydrides, tial, 1444 9248 correlation with nc=c,1439, 44 Simmons-Smith cyclopropanation with variation of M-C bond length, with zinc diiodomethane, ultra sound ap- trans-ligand-metal bond length, plication, 25108-109 1447-48 synthesis from aldehydes and zinc carbe- variation of M-C bond length, 1446-48 noids, 1299-100 with olefin substituent, 1446-47 .rl’-Olefins, formation of titanocene mono- Olefin transition metals, n bonds, k195-197 carbonyl complexes. 25361-363 Oligo(ferrocenylphosphine), 32155 Olefins, nickel-catalyzed oligomerization, Oligo(ferrocenylsilanes), 37:146, 148 12105-137 Oligomerization, of acetylenes catalyzed by catalyst preparation, 12107-114 supported nickel complexes, dimerization vs. isomerization, 12107 15224-226 importance of nickel, 12106 Oligosilanes, 3818 isomerization, 12123-125 cyclic, 3832 21 5 Organoaluminum rearrangements

linear, 3833, 36 in olefin polymerization, 17:281 Oligosilanyl anions, 3832-33, 37 nonsynthetic applications, 3869-74 Oligosilanyllithiums, linear, 3831-32 physical properties, 3860-61 Ollide ions, 888-91 reaction with metals, 3861-63, 65-69 rearrangements, 891 addition of water, 3870-71 a-Ollyl-metal complexes, 887-1 13 Direct Process Reaction, 3867-69, electronic spectra, 8108-109 74-75 magnetic susceptibility, 8104-105 Grignard reaction, 3866-67 NMR, 8106 Organic salts, carbene complex synthesis NQR, 8106 from, 25141-142 oxidation-reduction reactions, 8107-108 Organic synthesis One-carbon ligands, in triosmium clusters, via alkynes and carbonylcobalt com- 265-58 plexes, l2366-371 One-electron transfer reactions, computer with a-allylic nickel complexes, 829-83 representation, 26195-197 with nickel carbonyl, fk40-48 in allyl-alkyl cross coupling, 26203, 205 via intermediate organocopper com- Onium salts, 8:125 pounds, l2301-310 syntheses, 106 via organometallics, 10327 Optical activity, of organo-transition-metal stoichiometric and catalytic syntheses, complexes, 18151-205 l2:369 Optical induction, 18186-189 Organoactinide complexes, 9382-391 Optical Kerr gate, third-order nonlinear op- allyls, 16249-250 tics analysis, 43:363-365 Organoaluminum compounds Optical power limiting, 43356-358, complexes with fluorosilanes, 9:268 398-341 cyclic fluorides, 9344 Optical purity, of chiral metal complexes, in olefin metathesis, 16284 1k166-168 phosphinates, 9345 Optical resolution, 18153-165 rearrangement of unsaturated species, of diastereoisomers, 18160-165 1669 of enantiomers, 18153-160 allylic, 1691-98 Optical rotatory dispersion spectra, of chi- carbalumination, 1698-106 ral metal complexes, 18192-193 pericyclic processes, 16:71-72 Optical yields, in synthesis of cyclopro- role of intermediates, 16:72 panes, 18156-157 sulfoximides, 9347 Orbital energies, in cyclopentadienylgerman in Ziegler-Natta process, 16256-260 ium complexes, 26:263 Organoaluminum compounds, exchange re- Orbital symmetry rules actions, 8179-187, 193-198,201-202 and rearrangement of organomagnesium alkyl derivatives, 8179-183 compounds, 16153 cyclopropyl compounds, 8:183-185 and 1,2-shifts in ring whizzers, 16223 organo-Group I1 compounds, 8186-187 Organic bridging group complexes, 355-7 pyridine-catalyzed reactions, 8185-186 Organic chemistry, transition metals, unsaturated derivatives, fk183-185 U:1-27 Organoaluminum hydrides, reduction of or- Organic fluorides, 3860 ganolead compounds, R270 Organic halides, 3859-60,74-75 Organoaluminum rearrangements, 1691- adsorption on metal surfaces, 3863-65, 98, 111-130 73 alkylaluminum exchange, 16116-117 as catalyst activators of allylic species, 16:91-98 in codimerization of ethylene and buta- formation of derivatives, 1694-97 diene, 12279-283 isomerization, 1691-94 Organoaluminum rearrangements 21 6

kinetic vs. thermodynamic control, thermochemistry, 4228-229 1697-98 UV spectra, 4223-227 of dimeric alkyls, 16:103-106 Organoarsine oxides, 9:280-281 exchange reactions, 16116-120 coordination compounds, 9284 of addition compounds, 16:118-120 Organoberyllium compounds, 7A1, 8170- involving dissociated species, 171, 9:195-253 16116-1 18 alkali metal complexes, 9:240 intermolecular exchange, 16125-126 alkoxides, 9230 intramolecular exchange, 16120-125 alkyls, 9219 activation parameters, 16121-122 coordination complexes, 9221 in symmetrically bridged systems, amino-alkyls, 9222 16:123 adducts, 9227 in unsymmetrically bridged systems, amino derivatives, 9248 16:120-123 anionic halide complexes, 9239 involving metal-multiple bond interac- equilibria in solution, 9233, 237, 239 tions, 16:126-129 NMR spectra, 9217-219 Organoantimony compounds 0x0 derivatives, 9230, 250 hcxacoordinate species, 14188-191 silanol derivatives, 9286 cis-trans isomerism, 14188-189 thiol derivatives, 9236 IR studies, 14189-191 Organoberyllium hydrides, 9241, 243-250 NMR studies, 14189-191 complexes, 9242 synthesis, 14188-189 preparation, 9243 X-ray studies, 14189-190 properties, 9245 pentavalent species, 14188 reactions, 9247 tertiary stibines, 14197-202 with olefins, 9248 triorganostibine sulfides, 14192-197 Organoboranes, 1330-31 Organoarsenic compounds, 4145-229, 13:7, alkyl exchange reactions, 2258-261 12-13 thermal isomerization, 2261-262 arsines, 4182-183 1-alkynylboranes, 39366-367 arsonium compounds, 4159, 168-169, allyl- and benzylboranes, 39360, 368-369 173-174 arylboranes, 39367-368 dipole moments, 4213 diborane(4) derivatives, 39373-374 ESR spectra, 4223 methyleneboranes, 39371-373 geometrical isomerism, 4214-218 methyleneborates, 39:370-371 ionization potentials, 4227-228 reactions, 1M4-15 IR spectra, 4220-222 vinylboranes, 39:356, 359, 364-366 NMR spectra, 4222-223 Orgdnoboron compounds optical isomerism, 4214-218 bond dissociation energies, 2106-107 poisoning by, 1322-25 reaction mechanisms, 4309-324 polarography, 4228 addition reactions, 4321-322 radiochemical studies, 11:221 bond cleavage, 4310-321 Raman spectra, 4220 neighboring group participation, resolution, 4:214-218 4:323-324 structures, 4199-220 redistribution reactions, 4309-310 bond angles, 4212 thermal stability and disproportionation, electron diffraction, 4:210-212 10:249 microwave spectroscopy, 4210-212 Organoboron rearrangements, 1668, 72-91 X-ray determinations, 4199-210 allylic derivatives, 1672-73 synthesis, 4146-173 cyclic allylic derivatives, 1673-78 thermal decomposition, 4173-174 cycloaddition, 1680-82 21 7 Organocopper complexes

cycloreversion, 1680-82 aldehydes, 2300-301 migration in tetracoordinate species, alkynes, l2:28-299 1682-91 allenic phosphine oxides, l2297-298 1-alkynylborates, 16:87-88 allylic acetates, 12:294-296 chemically induced, 16:82-84 isocyanates, 2300 with deboration, 1668-91 ketones, 2300-301 photochemically induced, 1684-88 nitriles, 2300 with retention of boron, 16:82-88 nitrones, 12500 tetraarylborate salts, 16:85, 87 olefins, 2296-297 thermally induced, 16:82-84 propargylic acetates, l2293-296 orientation, 16:71 propynoates, 12.299-300 pericyclic processes, 1671-72 a#-unsaturated carbonyls, l2290-293 role of intermediates, 16:71-72 dimerization reactions, l2254-259 sigmatropic, 1672-82 via thermal decomposition, 12:255 skeletal, 1671 halogenation, a289 skin, 1671 infrared studies, 12239-240 Organocadrnium compounds, 8:174-175 as intermediates in organic synthesis, exchange with organo-Group I1 com- l2301-312 pounds, 8:176 addition to olefins, l2307-310 phosphine imines, 9286, 288 Ullmann reactions, l2301-307 silanol derivatives, 9286 order of reactivity, 2252 Organochromium(II1) complexes, 38:160 oxidation reactions, 12:254-259 Organocobalt complexes, 1k331-441 preparation, 12:216-231 acid-base equilibria, 1k396-397 by copper-halogen exchange, catalytic hydrogenation, 1k435 2223-224 comnoids, 1k384-386 from copper salts and organometallics, u-n equilibria, 11:399 12:217-223 halogenation, 1k425 decarboxylation of copper(1) carboxyl- macrocyclic complexes, 11:386 ates, a226 nitrosation, 1k425 by metalation reactions, l2:224-225 nomenclature, 1k336-341 via organozinc compounds, 2222-223 preparation, 1k350-383 reactions from cobalt(1) complexes, 1k351-358 with diazocompounds, a290 from cobalt(I1) complexes, 1k358-360 with 1,3,5-trinitrobenzene, U289 from cobalt(II1) complexes, 1k360-361 reduction, 2253-254 reactions, 1k396-400 stabilization effects, 2240-252 photochemical, 1k403 of aggregation, 2251-252 reduction, 11:432 organic substituents, l2243-244 stereochemistry, 1k343-349 other ligands, 12.240-243 configuration of cobalt ion, 1k343 structure, U:231-240 isomerism, 1k348 substitution reactions, l2259-290 organic ligand, 1k347 acid halides, l2:278-283 structural studies, 1k344 alkyl halides, l2262-266 transalkylation reactions, 1k421-424 allenyl halides, U26-267 to mercury, 1k421 ally1 halides, 2266 Organocopper complexes, 2215-313 aryl halides, 12:274-278 addition reactions, 12.290-301 arylsulfenyl halides, 12285 acetylenic phosphine oxides, esters, l2287-288 12~297-298 1-haloalkynes, 2278 acrylates, 2297 oxiranes, l2288-289 Organocopper complexes 21 8

polyhaloalkanes and -enes, U:269-274 carbenes, 2059-61 propargyl halides, 12266-267 bis(complexes), 2059 silicon halides, 12:267-269 formamidine formation, 2059-60 thermal decomposition products, and hydroxide, 2060 1224-251 from isonitriles, 2059 dimerization, 12:249-250 oxidative addition of iodine, 2059, 64 disproportionation, 12:246-249 carbonylchloride, 2061-62 free radical, 12245-246 back-bonding, 2062 heterolysis, 12250-251 substitution reactions, 2069 Organocopper compounds, 244-45 and zinc aryls, 2055 Organocopper(I1) compounds, 12312-313 comparison with other metals, Organocopper ylide complex, 12230 20101-105 Organodiboron derivatives, containing bo- cyclo-octadiene, 2049-50 ron-boron bonds, 10237-269 cyclo-octatetraene, u):50 heterocyclic derivatives, 10244-245 u-cyclopentadienyls, 2052-55 preparation, 10238-247 fluxionality, 2052 thermochemical properties, 10248 dialkyl anions, 2041-42 Organodichlorophosphine, 32154 oxidative addition, 2066 Organoelement chemistry, 10303 diary1 anions, 2042 Organogallium compounds, 8187-190 P-diketonates, 2051, 105 bonded to transition metals, 16117-118 ethylene, 2051 exchange reactions, 16:117-118 ferrocenyl derivatives, 2052-53 cyclic hydroxides, 9344 with gold-gold bonds, 20:53, 95-96 dimeric species, 16:113 protonation, 2053 exchange with organo-Group I1 com- pounds, &190 gold-carbon bond cleavage, 2069-72 phosphinates, 9346 hydride, 2072 Organogermanium compounds imines, 2070 1.2-anionic rearrangements, 161-31 iminomethyl trimers, 2060-61 catenation, 438-47 oxidative addition, 2061, 65 early history, 92 insertion reactions, 2066-69 Organogermanium-nitrogen compounds, acetylenes, 2067-68 3398-412 fluoroolefins, 2067 cleavage of Ge-N bond, 3408-412 sulfur dioxide, 2069 heterocyclic nitrogen derivatives, isonitriles, 2058-61 3405-407 cations, 2058-59 prcparation, 3398-407 NQR spectra. 2058 reactions, 34077412 reactions with alcohols and amines, Organogermanium radical anions, 13276 2059 Organogermylamines, 3400-405 ketenide complex, 2049 Organogold compounds, 244 mono-olefins, 2050 Organogold(1) compounds norbornadicne, 2050 acetylenes, 2051 oxidative addition, 2064-66, 84 acetylides, 2048-49, 68 of alkyl halides, 2066 aryls, 2054-58 gold(I1) intermediates, 2065-66 clusters, 2056-58 of halogens, 2064-66, 87 with gold-gold bonds, 2054 via thallium(TI1) compounds, 2065, via lithium aryls, 2056 76-77. 84, 87 oxidative addition, 2064-65 phosphine alkyls, 2042-46, 66 zinc derivatives, 2055 via aromatization auration, 2045 21 9 Organo-Group I aryl migrations

binuclear bridged compounds, gold-carbon bond cleavage, 2093-94 2043-44 insertion reactions of sulfur dioxide, via diazomethane, 2045 24k92-93 via gold oxonium salts, 2045 isomerization, 2090-92 phosphine exchange, 2043 ligand substitution, 2093 phosphine aryls, 20:44-45 mixed alkyls, 20:41 phosphine clusters, 2062 via oxidative addition to gold(I), photolysis, 20:63-64 2064-66 radical chain reactions, 20100 monoaryls, 2086-88 reactions with platinum(I1) analogues, 20101-103 acetylenes, 20100 reactions organoplatinum(I1) compounds, 2071 with acetylenes, 20100 sulfur dioxide, 20100 with sulfur dioxide, 2092-93, 100-101 thiols and selenols, 2094 reductive elimination, 2089-90 triosmiumdecacarbonyldihydride,2&72 of alkane, 20:89-90 thermal decomposition, 2063 similarity to gallium(II1) compounds, coupling of organic Iigands, 20:63 20105 three-center, two-electron bonding, tetraalkyl anions, 2073 2052-58 tetraaryl anions, 2073 trans-influence, 2095 trans-influence, 20102 tris(o1efin) cations, 2050-51 trialkyls, 2075-76 vinyls, 2049 phosphine adducts, 2075-76 with gold-gold bonds, 2054 triaryls, 2075-77 X-ray structures, 20:94-95, 98 X-ray structure, 2096-98 gold-carbon bond lengths, 2095 ylides, 2073-75, 78, 90, 103 gold-gold bond lengths, 20:96 bond lengths, 20:97 ylides, 2046-48, 103-104 polymers, 20104 in arthritis therapy, 20:47 protonation, 2073-74 binuclear derivatives, 2047-48 Organo-Group I aryl migrations oxidative addition, 2065-66 in anions, 16170-193 zinc derivatives, 2086 competition Organogold(I1) compounds, 2065-66 between ally1 and phenyl migration, ylides, 2078 16205 Organogold(II1) compounds, 2072-94 between phenyl migration and cleav- acetylene, 2088 age of benzyl, 16:202-206 bis(carbene), 2086 experimental techniques, 16169-170 structure, 20:87 solvent choice, 16:169-170 carboranes, 2088 intermediacy of spiro anions, 16187-193 comparison with other metals, in 1,2-migrations, 16176-177, 189 20101-105 stability, 16188-189 cyclo-octadiene, 2088, 103 in intermediate radicals, 16:193-196 from dialkylaurates and alkyl halides, mechanism, 16194-195 2041 kinetics of rearrangement, 16202 dialkyls, 2078 I,2-migrations, 16170-180 a-amino acid complexes, 2082 via carbanions, 16175 anions, 2084-85 mechanisms, 16:173-180 cations, 2082 solvent effects, 16178-179 dimeric halides, 20:78-79, 81-83, 101 spiro intermediates, 16176-177 dithiocarbamate, 2082 1,3-migrations, 16181-184 tetrameric hydroxide, 2080 1,4-migrations, 16184-186 Organo-Group I aryl migrations 220

catalysis by potassium tertiarybutoxide, Organolead fluorides, 9265 16:185-186 Organolead hydrides in competition with protonation, 16186 with Pb-N bond, 2289-292 1,5-migrations, 16186-187 with Pb-0 bond, 2296 in radical anions, 16196-202 preparation, 2266 or benzenes, 16200 properties, 2269, 272-274 of naphthobicyclobutane, 16198 reactions with diazoalkanes, 2279 of 1,1,3-triphenylindene, 16196-198 as reducing agents, 2274-275 Organo-Group I11 compounds, 16112-120 mechanism of reduction, 2279 exchange reactions, 16116-120 Organolead ketenimines, 2283-284 of addition compounds, 16118-120 Organolead-nitrogen compounds, 3440-443 involving dissociated species, Organolead oxides and hydroxides, E296 16116-118 alkoxides, 2298-299 monomer-dimer equilibrium, 16115-116 ligand exchange, 2300 stability of dimers, 16:115 protolysis, 7:300 structure and bonding, 16112-115 peroxidcs, 2299 electron-deficient bridged structures, Organolithium compounds, 3365-393, 27- 16113 11, 15255-262 tetraalkyl anions, 8196-198 acid-base behavior, 3383-384 Organo-Group IV compounds association in solution, 3373-374 reactions with BzX4, 10261 bonding, 15260-262 syntheses of organodiboranes, 10:247 lithium-hydrogen interactions, Organo-Group V compounds, 1056 19261-262 Organohalopolysilanes, synthesis metal-metal interactions, 15260-261 from alkoxypolysilanes, 624-25 complex derivatives, 3384-387 by chlorodemethylation and related reac- conversion to Grignard reagents, 7:lO tions, 620-24 degree of aggregation, 19255-258 by cleavage of polysilanes with halogens, dipole moments, 3376 625 discovery, 63 from Si2CI6,626 electronic structure, 3377-380 from silanes, 6:25 exchange reactions, 8168-170 Organohalostannanes, 32163 with organo-Group I1 compounds, Organoindiuni compounds, 8190-191 8177-179 Organolanthanides, 9365-382 heats of formation, 3380-381 alkyls, 9365 interaction with Group I1 compounds, allyls, 16249 15265-266 aryls, 9366 interaction with Group 111 metalates, cyclopentadienyls 19263-265 divalent, 9378 IR spectra, 3374-375 trivalent, 9367-376 mass spectra, 3:371-372 adducts, 9370-372 NMR spectra, 3381-383 chlorides, 9372-376 l3C NMR spectra, U:142-143, 169 indenyls, 9376 preparation, 3366-368 Organolead compounds, 2242-303 properties, 3366-368 catenation, 463-77 reaction mechanisms, 3387-393 reaction with hydridic reducing agents, carbanion rearrangements, 4:273-277 2267-268 configurational stabilities, 4:271-272 structure and reactivity, 2243 metal-halogen exchange, 4269-271 water soluble. 231 metal-hydrogen exchange, 4272 Organolead(I1) compounds, 19:123, 153 Wurtz coupling, 4:278-280 Organomagnesium compounds

reactions with polyhalo compounds, 246 Lewis acid-Lewis base interactions, structures, 3368-371, 19258-260 32153-154 synthesis, 39:2 lithium analogs, comparison with, 32:152 Organolithium polymerization catalysts, Mg2Cz ring, 32153 1lk55-97 Mg vs. ether oxygen, geometric relation, aggregation state, 1871-72 32156-157 effect of donor ligands, 1859 orbital interactions, role of, 32154 and mechanism, 1872-73 polymeric structures, 32153 diene-olefin copolymerization, 18:78-79 R-0-R ether groups, orientation of, solvent effects, 1878-81 32154-155 for dienes. 1856-57, 65-78 sp hybridization, 32154 mechanism, 1865-78 steric hindrance, 32154 and living polymers, 1860 Organomagnesium compounds, gas phase I3C NMR studies, 18:67 structures for olefins, 1856-57, 60-65 compounds measured, 32158 kinetics for ethylene reaction, 1862-65 crystalline state, comparison to, 32157 mechanism, 1860-65 gas phase electron diffraction (GED), with polar ligands, 1865-71 32157-159 bis(diphenylphosphino)ethane, low volatility, 32157-158 1870-71 X-ray scattering, 32159 Organomagnesium compounds, reaction effect of reaction conditions, 1865-66 mechanisms, 4280-289 effect on polymer microstructure, addition to ketones, 4285-288 1866, 69-71 addition to nitriles, 4288-289 mechanism of action, 1865-71 bonding, 4280-281 TMEDA, 1866-69 Grignard reagent, structure, 4280-281, in polymer grafting, 1886-89 283-285 in reparation of telechelic polymers, reaction with transition metals, 4281-283 18~89-93 Organomagnesium compounds, solid state structure and reactivity, 1859-60 structures telomerization of benzene and ethylene, cyclic, 32:169-171 1861 cyclopentadienyl derivatives, 32195-197 Organolithium reagents, in direct arylation dicoordination, 32:171-173 of Pd or Pt complexes, 28:221-226 dimeric, 32159-166 Organolithium sandwich complex, 26:219, hexacoordination, 32:173-175 223 intramolecular coordination, 32184-195 Organomagnesium compounds magnesium anthracene derivatives, background, 32147-150 32197-201 importance, 32149-150 magnesium-transition metal bond com- via metal atom synthesis, 15105 plexes, 32208-211 Mg-C, 32149-150,152 main group metals, complexes with, Organomagnesium compounds, bonding 32203-208 aggregation, tendency of, 32153 mixed metal complexes, 32203-211 complex formation, 32153 monomeric, 32159-166 coordination geometry, 32153-154 nontetrahedral coordination, 32171-175 dihalides, hexacoordination of, 32156 organic anions, delocalized, 32195-203 disorganylmagnesium molecule, 32153 pentacoordination, 32173-175 electronegativity, 32152 polyethers, complexes with, 32175-184 electronic configuration, 32152 polymeric, 32166-169 geometrical constraints, 32156 simple ligand complexes, 32184-188 Organomagnesiurn compounds 222

tetrahedral coordination, 32159-171 in reactions of ally1 Grignards with sty- tricoordination, 32171-173 rene, 16138-139 unsaturated ligand complexes, 32201-203 ring cleavage vs. ring size, 16148 Organornagnesium compounds, structural 12-shifts, 16162-163 developments aryl migration, 16163 conformational constraints, 3215 1 and solvent polarity, 16148, 151 diphenylmagnesium, 32151-153 substituent effects, 16:148-149 di(p-tolyl)magnesium, 32151-153 transition state geometry, 16155-160 hexacoordinated state, 32151 Organomercury compounds, 8176, intramolecular coordination, influence of, 1O:lO-12 32151 camphenilone derivative, 1023 intramolecular solvation, 32151 from organocobalt complexes, 1k421 lithium-halogen exchange, analogy to, reaction mechanisms, 4289-309 32152 as carbene sources, 4308-309 metallation, 32152 cationic species, 4294-297 unsolvated compounds, 32:150-151 exchange, 4292-294 1,3-xylyl crown ethers, 32151-152 low-valent species, 4289-290 Organomagnesium rearrangements, oxy-and deoxymercuration, 4298-304 16131-165 symmetrization reactions, 4290-292 allylic compounds, 16:160-162 stereochemistry of reactions, 1027 photochemical cyclization, 16161-162 in treatment of disease, 1323-24 cyclopropyl derivatives, 16:131-135 Organomercury derivatives, of silanols, kinetic studies, 16135-136 9286 in dimerization of 1,3-hutadiene, 16145 Organometal carbonyls, 89 equilibria in cyclization-cleavage re- Organometallic chemistry arrangements, 16145-148 historical perspectives, 131-38 dependence on enthalpy changes, interaction with biological sciences, 1333 16:145- 147 Organometallic chemistry, steric effects dependence on ring strain, 16145-148 electronic profiles, 36142-143 stabilization of four-membered rings, steric effect quantification, 36137-141 16147 distance variation, 36137-138 stabilization of three-membered rings, possible interactions, 36138 16146- 147 solid cone angle, 36141 halogen dependence, 16148 spatial ligand variation, 36138-140 in intermolecular addition to alkanes, Tolman cone angle, 36140 16136-137 vantage point choice, X140 via intramolecular addition and ring steric profiles, 36142-144 cleavage, 16131-135 QALE approach, 36142-144 kinetics, 16148 steric size measurements, 36152-153 mechanism, 16149-155 threshholds, 36:142-145 birnolecular carbanionic, 16154 Organometallic clusters, containing oxygen via B complexes, 16153-154 atoms, 28369-382 concerted four-center, 161.50, 152 Organometallic complexes via heterolytic Mg-C bond cleavage, containing oxygen, see Organometallic 16149, 151 0x0 compounds via homolytic Mg-C bond cleavage, with ketene ligands, 2816-20 16149, 151 synthetic methods, m21-32 via initial electron transfer, 16149-151 oxidation with dioxygen, 28339-340 via magnesium transfer, 16149-151 reaction with ketenes, addition to metals 223 Organometallic compounds

to form stable ketene complexes, dimerization, 3271 283 insertion, 3262-63 unsaturated, ketene addition to, 2821-22 carbonyl, reactions with, 3242 Organornetallic compounds complex rearrangement, 3229 chromium deprotonated bridging ligands, acetylene, insertion, 32:72 3227-32 carbene, reactions with, 3243-44 desulfurization, 3214-15 carbon diselenide, addition, 3267 dithiaheterocycles carbon disulfide, addition, 3266, 68 formation, 3239 carbonyl, reactions with, 3241-42 fragmentation, 32:39-40 carbyne, reactions with, 32:46 dithioacetals, reactions with, 3214 cyclization, 3230 episulfides, thermal fragmentation, deprotonated bridging ligands, 32:30 3238 diazo compounds, reactions with, 3297 Fe(CO),], 323-5, 8, 33, 40 dithioesters, 3249 [Fe,(CO),], 323-6, 8, 16, 40 heterocyclic carbenes, 3258 (OC),Fe-Fe(CO),, 323 selenocarbenes, reactions with, 32:22 orthometallation, 328 thioaryl chlorides, reductive dimeriza- reactions with thiones, 32:4-6 tion, 3248-49 selenadiazoles, reactions with, 3218-19 thiocarbenes, reactions with, 3222 thiadiazoles, reactions with, 32:18-19 thiols, 32:37 thietes, 3220-21 cobalt thioacyl, reactions with, 32:91-92 acetylenes, cycloaddition, 32:75 thiocarbenes, reactions with, 3221 carbon diselenide thioketenes, 32:35 dimerization, 3269 thiolate formation, 32:57-58 insertion, 32:64 thiols, 32:36-37 carbonyl, reactions with, 32:42-43 thiophene, reactions with, 3214-15 seleaadiazoles, reactions with, 32:19 trichloromethyl thioalkyls, 3250 thietes, 3220-21 trithiocarbonates, rearrangement of, thioaldehyde oxidation, 32:16 3240 thiocarbenes, reactions with, 3221 manganese thioketones, 3234 acetylenes, cycloaddition, 3274-75 thiones, reactions with, 3210 carbyne, reactions with, 3246-47 xanthates, desulfurization, 3240-41 desulfurization, 329 gold, carbon disulfide, alkylation, diazo compounds, reactions with, 3297 3283-84 isothiocyanates, 32:36 halogen-metal exchange reactions, thioaroylchlorides, reactions with, 3212 7:19-21 thioaryl chlorides, reductive dimeriza- iridium, carbon disulfide, insertion, 3262 tion, 3248 iron thioketones, 3235 acetylene, reactions with, 3247 thiones, reaction with, 32:Y acetylenes and ethene, reactions with, thiophene, reactions with, 3294 32101 mass spectra, 8211-237 acyl-thioether chelate, photolysis of, metalation reactions, 7:15-19 3224 via metal atom synthesis, 1553-107 allene, reactions with, 3247 metal-metal exchange reactions, 72-25 carbenes, reactions with, 3287-89 molybdenum carbon disulfide acetylenes and ethene, reactions with, addition, 3266 32101 alkylation, 3283-85 carbon disulfide, dimerization, 3269 Organometallic compounds 224

carbyne, reactions with, 3245, 55-56 rhenium episulfides orthometallation, 329 desulfurization, 3238 thiones, reactions with, 329 thermal fragmentation, 3238 rhodium fulvenes, reactions with, 3220 carbon diselenide thioesters, reactions with, 32:ll alkylation, 3286 thioketones, reactions with, 32:11 dimerization, 32:69 thiolactones, reactions with, 3211-12 carbon disulfide, alkylation, 3286 nickel rubidium carbon disulfide, dirnerization, 32:71 acetylenes sulfur ylid, decomposition of, 3226 cycloaddition, 3278-79 thioethers, 3233 and ethene, reactions with, 32101 niobium, thioketenes, 3235 carbon diselenide, insertion, 3264 osmium carbon disulfide, insertion, 32:62-63 acetylenes, cycloaddition, 3278 ruthenium, thiols, 3236 carbon disulfide, insertion, 32:62, 65 solvent coordination effects, 7:30 decomposition, 3215 syntheses via diazonium salts, 104 oxidative addition, 3215-16 titanium rearrangement, 32:lS-16 acetylenes and ethene, reactions with, ring opening, 32103 32101 selenoformaldehyde, 3223-24 carbon disulfide, dimerization, 32:71 thermal rearrangement, organosulfur, tungsten 32103-104 acetylene, insertion, 3272 thioacyl, reactions with, 3292 carbene, reactions with, 3243-44 thioformamide, reactions with, carbonyl, reactions with, 3241-42 3217-18 carbyne, reactions with, 3255 thioformyl complex, 3226-27 cyclization, 3230 thioketenes, 3236 deprotonated bridging ligands, 3230, thioketones, 32:34 32 thiophene, reactions with, 3215 dithioesters, 3249 UV irradiation, 32103 heterocyclic carbenes, 3258 vinyl sulfides, 3215-16 polychalogens, reactions with, 3296 pa 11 adi u m selenocarbenes, reactions with, 3222 acetylene, insertion, 3273-74 thermal rearrangement, organosulfur, carbon disulfide, insertion, 3265 32103 episulfides, 3237-38 thioacyl, reactions with, 32:91 mononuclear orthometallation, thiocarbenes, reactions with, 3222 3212-13 thioesters, reactions with, 32:11 oxidative addition, 3216 thioethers, 32:32 thioethers, reactions with, 3212 thioketenes, reactions with, 3293-94 thiolates, reactions with, 3212 thioketones, 3235 thiones, reactions with, 32:9 reactions with, 32:11 physiological action, 7:30 thiolactones, reactions with, 3211 platinum vanadium, acetylenes and ethene, reac carbon diselenide, dimerization, 32:69 tions with, 32:lOl carbon disulfide, alkylation, 3281 vanadocene, thiobenzophenone, reactions thiones, reactions with, 329 with, 17,3212 thiophene. reactions with, 32:15 zirconium trithiocarbonates, reactions with, 3210 carbon disulfide, alkylation, 3284 relative reactivity studies, 213 stilbene elimination, 3226 225 Organornetallic radical anions

a-thioalkyl complexes, 3225-26 carbonylmanganate coupling, thioketones, 3234-35 3373-76 zirconocene, thioaldehyde complex, carbonylmanganese coupling, 3216-17 33:73-76 Organometallic exchange reactions, 109 contact ion pairs, 3379-82 Organometallic films and composites, third- electron transfer, 3383-87 order nonlinear optics, 43390,392,394 contact ion pairs, electron-transfer equi- Organometallic heterocycles, 13:139-271 libria, 3387-96 aromaticity in, 13251-261 TPWCO)~. anthracene derivatives, 13258-261 as charge-transfer salts, 3391-93 6p-electron systems, 13252-256 contact ion pairs of, 3391-93 10p-electron systems, 13256-258 ion pairs, evaluation of, 3393-96 14p-electron systems, 13258-261 and pyrylium, 3389-91 photoelectron spectra, 13:251-252 spectral analysis, 3387-89 mass spectral studies, 13245-251 ion-pair annihilation comparison with carbocyclic data, electron-transfer processes, 33101-106 13245-246 nucleophilic and electron-transfer pro- pyramidal inversion, 13243-245 cesses, competing pathways, in solid and gaseous states, 13228-233 33101-106 in solution, 13229 nucleophilic transfer processes, structural studies, 13223-245 3396-106 conformational inversion, 13235-243 nucleophilic adducts, 3397-98 radical dimers, 3398-99 conformation and substituent prefer- thermal decomposition, 33~99-101 ence, 13234-235 organometals, ionization potentials, of, effects of heteroatom, 13225-228 3353 Organometallic ions and ion pairs Organometallic ketenimines, bonding, bis(arene)iron(II)dications, 33106-118 7~135-136 charge-transfer structures, 33111-118 Organometallic nitrosyl complexes, 7:211- ferrocene 236, see also Nitrosyl metal complexes charge-transfer complexes with, Organometallic nitroxides, from hydroxyl- 33107-1 09 amine rearrangement, 1617-18 photoinduced electron transfer with, Organometallic 0x0 compounds 33109-11 1 acetylene, 28:351-356 carbonylmetallate anions carbonyls, 28351-356 electron donors, charge-transfer salts catalytic oxidation of olefins, 2tk341-342 IR spectra, 3358-60 clusters containing oxygen atoms, isolation, 3354-56 28369-382 photoexcitation, 3363-72 ligands in, 2lk340-341 salt effects, 3360-63 metal cyclopentadienyl complexes con- solvatochromism, 3360-63 taining oxygen, 28356-359 solvent effects, 3360-63 metal oxoalkyl compounds, 28347-351 spectral characterization, 3354-56 metal oxoaryl compounds, 28347-351 X-ray structures, 3356-57 olefins, 28351-356 thermal annihilation of, 3372-87 0x0 alkylidenes, 2tk351-356 carbonylcobalt 0x0 alkylidynes, 28:351-356 cations and anions, 3379-82 polyoxometallates, 28:382-387 coupling, 3376-79 preparation of, 28:342-347 dimer formation, 33232-83 Organometallic pseudohalides, 5169-224 carbonylcobaltate coupling, 3376-79 Organometallic radical anions, 15273-313 Organometallic radical anions 226

boron, 15276 in oxidative-addition reactions, Group 1 elements, 15274-275 14~383-388 properties, 15276 ESR evidence, 14384 via trimethylsilyl radicals, 15275 in reductive-elimination reactions, 14388 Group I1 elements, 15275 transition-metal compounds, 14363-366 Group IVB elements, 15276-310 carbonyl species, 14366 acylsilanes, 15306 ESR spectra, 14363 alkenyl derivatives, 15276 by photolysis of dimers, 14366 alkynyl derivatives, 19276 Organometallic reactions aryl derivatives, 15283-305 with hydronickel, palladium, and plati- benzheterocycles, 15291, 295-296 num complexes, 13273-361 Hiickel calculations, 15298-303 mechanisms, 4268-340 naphthalene derivatives, 15291, 294 Organometallic sonochemistry, see Sono- polyphenylenes, 13291-293 chemistry, organometallic polysilanes, 15305-306 Organometallic species, transient preparation, l5276-279 alternative methods for detection, reactions, 15276-279 25298-299 reductive coupling, 15283-286 electronic excited states of, 25285-286 silicon-nitrogen compounds, 15310 flash photolysis of metal carbonyls silicon, 15276-310 in gas phase, 25283 25284-285 tin, 15277 isomerization, 25281-283 transition metal complexes, 15311-313 in solution, unimolecular processes, 25284 of acetylenes, 19311 IR kinetic spectroscopy, 25299-311 bridgcd bimetallic species, 15311 dinuclear metal carbonyl species, ferrocenyl derivatives, 15312 25307-311 infrared studies, 15311-312 [CpFe(C0)2)2(Cp=~s-C2H5)r nonacarbonyltricobaltcarbon deriva- 25309-311 tives, 15313 Mn2(CO),,), 25308-309 14:345-392 Organometallic radicals, gas phase photochemistry, 25300-304 14391 actinide species, Cr(CO)6, 25303-304 generation, in homolytic substitution reac- Fe(CO)s, 25300-303 tions, 14370-381 photochemistry of Cr(C0)6 in solution of main group species, 14371-373 Cr(CO)s (H)*, 25306 of platinum derivatives, 14373-381 Cr(CO)S (H20),25307 of Group IV elements, 14352-363 Cr(CO)S (N2), 25307 ESR spectra, 14356-362 Cr(CO),( solvent), 25304-306 mechanism of formation, 14360-361 low temperature characterization tech- stable species, 14355-363 niques structure, 14354-355 low temperature solutions, 25280 transient species, 14352-355 matrix isolation, 25278-280 via UV irradiation, 14:352-354, 358 Organonickel complexes, in organic synthe- lanthanide species, 14391 sis, 12195-253 in metal-alkyl photolysis, 14389-390 acetylene tctramerization, 12199 in metal-alkyl thermolysis, 14388-389 acylation, 1T222-224 mctal-centered species, 14346, 349-366 aldehyde synthesis, 12224 not centered on metal, 14367-370 ketone formation, 12222-224 ESR spectra, 14367-370 via oxidative addition, 12222 metallocenes, 14368 alkoxylation, 12238-239 nitroxide derivatives, 14368-369 amination, 12239-240 227 Organoselenium compounds

of aromatic halides, 12239-240 propylene dimerization, 12205 of unsaturated compounds, 17:239-240 regioselectivity, 12205 butadiene oligomerization, 17:199 pseudo-Grignard reactions, 12217-224 ligand effects, 12199 with allylic acetates, 12220 carbon-carbon bond formation, effects of ligands, 17:220 1298-234 use of methanol, 12220 hydride-promoted reactions, reaction of butadiene with phenylhydra- 12204-208 zones, 12221 via metallacycles, 1R198-204 reaction of carbonyl compounds, 17:221 by oxidative addition and replacement reduction, 12235-237 reactions, 17:208-217 silylation, 12242-243 proton-promoted reactions, 12204- Organophosphine complexes, metal carbon- 205, 208 yls, 85, 8, 14 carbon-phosphorus bond formation, Organophosphine-imines, 9284-290 12243 Organophosphine oxides, 9:278-281 carbon-sulfur bond formation, 12243 coordination compounds, 9283 carbonylation, 17:225-234 properties and bonding, %279 acetic acid formation, 12233 Organopolysilanes, aliphatic, 6:19-110 of allene, 17:232 chemical properties cyclopentanone formation, 12233 alkoxy compounds, 632-34 cyclopentenone formation, 12233 halogen compounds, 6:26-31 effect of CO, 12234 synthesis hydride-promoted reactions, 12225, alkoxy compounds, 6:31 232 and insertion reactions, 12233 halogen compounds, 620-26 via metallacycles, 12225, 232 Organopolysilanes, photochemistry, via oxidative addition, 12225-227 1951-95 via polynuclear anions, 12232 Organoselenium compounds, reactions use of carbon dioxide, 12234 anionic compounds, 3243, 45-46 of vinyl halides, 12232 carbene complexes codimerization of butadiene and dicyclo- electrophilic attack, 32:43, 49 pentadiene, 12208 phenylethyneselenate addition, 3243 coupling of organic halides, 1R209-217 carbyne complexes catalytic reactions, 17:217 nucleophilic displacement, 32:45 saturated halides, 12216 phase-transfer, 3245 stereoselectivity, 12209, 215 rearrangement, 3245-46 use of Gngnard reagents, 12216 selenolate anions, 3245 vinylic halides, 17:215 cationic compounds, 32:49 cyanation, 17:224-226 dichloromethyl benzyl thioethers adiponitrile formation, 12224 chlorocarbenes, production of, 3250 aromatic substitution , 12224-225 iron, reaction with, 3250 dialkylfuran formation, 12220 diselenides, abstraction, 3249 genera1 considerations, 12195-198 electrophiles hydrogenation, 12235-237 acetylenes, 3272-79 of acetylenes, 17:235-236 acylation, 3283 of double bonds, 12235-237 alkylation, 32:86 of organic halides, 1R235 cycloaddition, 3272, 80 norbornadiene dimerization, 12199, 204 insertion, 3272 oxidation, 12235, 238 olefins, 3280 polymerization reactions, 12208 selenoacrylamide complexes, 3272 Organoselenium compounds 228

selenoaldehyde complexes, 3282-83, silylhydrazide anions, 167-14 86 NMR studies, 167-14 nucleophiles, selenoformaldehyde com- Wittig, 1618-24 plexes, 3292 mechanism, 1624 trichloromethyl thioalkyl compounds and a-silyl carbinol rearrangement, chlorocarbenes, production of, 3250 1620-22 reaction with iron, 3250 stereochemistry, 16:22-24 Organoselenium compounds, re- in synthesis of silyl carbinols, 1619 arrangement Organosilicon compounds, 4:2-38,324-339 metallacycles, decarbonylation, 3223-24 addition to unsaturated systems, selenadiazoles 4:335-337 decomposition of, 3218 anionic species, 4326-327 diselenolene complexes, 3219 asymmetry on silicon, 758 electron-withdrawing substitutents, bond cleavage, 4326-332 3219 catenation, 42-38 reactivity of, 3218 cyclic organosulfdiimides, 9347 treatment of, 32:19 early studies, 95 selenocarbons fluorides, 9263 a,p-unsaturated, 32:22 four-center processes, 4:333-334 decomposition of, 3222-23 neighboring group participation, Organoselenium derivatives of Group IV, 4:337-339 581-83 radical species, 4326-327 Organosilanes, 9:262 redistribution reactions, 4:324-326 Organosilicon Organosilicon compounds, in hiology, bond dissociation energies, 2:106-107 18:27S-330 chemistry, 39194 amino derivatives, 18285-286 ligands, 11:2S3-323 benzhydryl ethers, 18:286-287 heterocyclic derivatives, 1k293 as derivatives of active carbon com- radical anions, 15276 pounds, 18276-287 Organosilicon, 1,2-anionic rearrangements, activity comparison, 18277 16~1-31 detoxification, 18294-295 bis(organosilyl)hydroxylamines, 1614-16 as drug analogs, 18281, 283 infrared studies, 16:15 lipid solubility, 18282-283 catalyzed hydrazine rearrangement, and metabolism, 18294 16:4-7 natural occurrence, 18275 equilibration of isomers, 166-7 partition coefficients, 18282 mechanism, 16:4-6 pharmacological activity, 18276-283 heteroatomic, 16:3, 29 bulky trimethylsilyl group effect, homoatomic, 163, 27-29 18:271 hydrazines, 163-14 electronegativity effect, 18277, 281 aryl, 16:13-14 and trimethylsiloxylation, 18282-283 hydroxylamines, 1614-18 silatranes, 18291, 293-294 aryl, 1617 silicon substitution of carbon or nitrogen, nitroxide formation, 1616-18 18277-280 monosilylhydroxylamines, 1616 siloxanes, 18288-291 nitrogen to carbon, 1625-27 silyl groups as space fillers, 18281-283 rate of silyl group migration, 162 steroids, 18283-285 relative migration rates of silicon and car- without carbon analogs, 18288-294 bon, 16:13-14 Organosilicon compounds, charge transfer silicon to carbon, 1624-25 complexes 229 Organosilyl-substituted a-ligands

allylsilanes, 34152-154 Hammett study, 1639-40 aroxymethylsilanes, 34178-183 kinetics, 1638 arylsilanes, 34155-170 mechanism, 1641-45 arylsilylethers, 34178-183 solvent effects, 1639 charge-transfer(CT) complexation, stereochemistry 34149-152 at silyl group, 1640-41 1,l-dialkyl-1-silacyclobutanes, 34191-194 at stationary carbon atom, 1k41 ethynylsilanes, 34155 stereoelectronic requirements, 16:45 Group IV arylmetals, 34172-173 silyl silylmethyl thioethers, 1645 hetarylsilanes, 34170-172 squaric acid bis(trimethylsilyl)ester, Koopmans approximation, 34150 1658-60 organosilicons mechanism, 1659-60 as donors, 34:152-198 I3C NMR studies, 1658-60 as electron acceptors, 34199 tris(silyl)hydroxylamines, 1656-58 peralkyl polymetals, M194-198 mechanism, 1657-58 peralkyl polysilanes, 34:183-191 Organosilicon groups, as protecting groups, silyl ethers, M174-178 15116-117 silylsulfides, 34174-178 Organosiloxanes, 9261, 302-308 vinylsilanes, 34: 152- 154 Organosilver compounds, 244 Organosilicon, dyotropic rearrangements, Organosilyllithium compounds 1635-63 from chlorosilanes, k98 allyl silylmethyl esters, 1647-52 reaction with decaphenylcyclopentasilane, crossover experiments, 1648 k129-130 intermediacy of radicals, 16:48-49 Organosilyl-substituted a-ligands, mechanism, 16:50-52 15113-139 secondary deuterium kinetic isotope ef- acetylene derivatives, 15137-139 fects, 1649 bridging, 15138-139 solvent effects, 16:49 monodentate, 15137-138 stereochemistry azulene derivatives, 15136-137 allyl group migration, 16:48 migration of silyl groups, 15136-137 silyl group migration, 1650 classification, 15114-115 structural effects on migration, cycloheptatriene derivatives, 15132-134 1647-48 migration of silyl groups, 15132-134 benzyl silylmethyl ethers, 1652-55 cyclooctatetraene derivatives, 13134-135 anchimeric assistance, 1652 migration of silyl groups, 15134-135 ESR studies, 1653-54 transannular cyclizations, 15134 intermediacy of radicals, 16:53-54 effects of organosilyl group, 15115-119 mechanism, 1654-55 five-electron donors, 15126-131 structural effects on migration, cyclohexadienyls, 15130-131 1652-53 cyclopentadienyls, 15126-130 1,2-bis(silyl) derivatives, 1635-47 four-electron donors, 15122-126 of ethane, 1645-46 cyclobutadienes, 15122-123 bis(silyl)hydroxylamines, 1655-58 cyclohexadienes, 15124 mechanism, 1657-58 cyclopentadienones, 15125 N,N-bis(trimethylsily1)-o- silacyclohexadienes, 15125-126 allylhydroxylamine, 1655 silacyclopentadienes, 15124 1,4-double migrations, 1646-47 pentalene derivatives, 15135-136 other u-cexchange reactions, 16:60-62 via transannular cyclization, 15135-136 silyl silylmethyl ethers, 1636-45 six-electron donors, 15:131-132 crossover experiments, 1638 arenes, 15131-132 Organosilyl-substituted digands 230

thermal stability, 15115 benzyl methyl sulfide complex, 3273 three-electron donors, 15121-122 (CF,),C=N--C(O)R, 3280 allyls, 15121-122 7-coordinated dithioformates, 3272 two-electron donors, 15119-121 7-coordinated vinyls, 3272-73 carbenes, 15119-120 cyanocarbene complexes, 3282 isocyanides, 15119 cycloaddition, 3272, 76, 80 olefins, 15120-121 dithiocarbenes, 3285 Organostannoxanes, 5159-165 dithioester complexes, 3280 polymeric organotin oxides, 5164-165 dithioformate complex, 3272 structures, 5161-164 dithiolene complexes, 3276 Organostibine oxides, 9:280-282 electronic features, 3277-78 Organosulfur compounds, reactions Ruoroalkynes, 3274,76 acetylene complexes, 3247 insertion, 3272,74-75, 106 allene complexes, 32:47 metal thiolate complexes, 3274-75 anionic compounds. 3241-48 olefins, 3280 carbamates, 3241 PhC=N-NPh, 3278 carbene complexes protonation, 3280 benzothiazole, 3244 rearrangment, 3280-84, 86 displacement, 3244-45 reductive elimination, 32:74 elcctrophilic attack, 3243 sulfonium salt complexes, 3281 phenylethynethiolate addition, 3243 thioacetaldehydes, 3284 ring opening, 3243 thioacrylamide complexes, 3272 thioacetals, 3243 thioaldehyde complexes, 3280, 82-83 thiolates, 3244 thioethers, 3284 thiones, 3244 thioketene complexes, 3286 carbonyl complexes vinyl complex, 32:72-73 thioacetals, 3241-42 episulfides a-thiocarbanions, 3242 desulfurization, 3238 thioesters, formation of, 3242, 105 ring opening, 3237 carbyne complexes thermal fragmentation, 32:38 nucleophilic displacement, 32:45 isothiocyanates, 32:35-36 phase-transfer, 3245 neutral complexes, 3232-41 rearrangement, 3245-46 nucleophiles reductive deamination, 3246-47 addition, 3287-89, 93 sulfur insertion, 3246, 105 aminocarbyne complex, 3290-91 thiolate anions, 3245 base treatment, 3289 thione formation, 32:46 carbene complexes, 3287-90, 107-108 cationic compounds, 3248-50 7-carbene ligand, 3290 disulfides, abstraction, 3249 carbyne complexes, 3291 dithiaheterocycles decomposition, 3294 formation of, 3239 heterocyclic chelates, 3291 fragmentation, 32:38 7-ketenyl complex, 3291 dithioester complexes, formation of, metallacyclic, 3287 3249 phosphine, 3288 dithioesters. 3241, 105 protonation of, 3293-94 electrophiles rearrangement, 3288-89 acetylenes, 3271-79, 10.5-106 thioacyl, 32:91-94 acylation, 3283 thioaldehyde complex, 32:93 alkylation, 3280-84, 86, 107 thiocarbyne complex, 3289, 91 alkyl thiolate complex, 3275 thioformyl complex, 3292 231 Organotellurium compounds

thioketene, 32:93 thioformyl complexes, 32:26-27 thiophene complex, 3294, 108 thioketenes. 3211 thioaryl chlorides thioketones, 3216-17 decomposition, 32:48 thiolactones. 3211 rearrangement, 3248 thiolates and thioethers reductive dimerization, 3248 ligand exchange reaction, 32:13 thiocarbonates, 3240 mononuclear orthometallation, 32:12 thioethers thiones ferrole complex, 3232-33 aromatic orthometallation, 32:8 oxidative addition, 3233, 104 cobalt carbonyl, 3210 sulfonium salt, formation of, 3232 desulfurization, 32:3, 8 sulfur ylide, formation of, 32:32 as electron donors, 327-8 thioether complex, 3232 fragmentation of, 3227-32 thiophene, 32104 hydrogen migration, 323 thioketenes, 32:35-36 iron carbonyl complexes, 323-9 thioketones nonaromatic, 3210 aliphatic, 3234 (OC),Fe -Fe(CO),, 323 aromatic, 32:34 orthometallation, 329-10 substituted thiobenzophenones, 3235 product types, 324-6 thiobenzophenone, 3234 sulfur-containing ligands, 327 thiols, 3236-37 thiobenzophenones, 329 vinylidene complexes, 3241 thioketenes, 327-8 xanthates, 3240-41 UV irradiation, 32:3 Organosulfur compounds, rearrangment thiophene, 3214 complex thiones, 321 1 vinyl and ally1 sulfides dithioacetals, 32:14 oxidative addition, 32:15 dithiocarbenes photolytic decomposition, 3215-16 cx,D-unsaturated, 3222 thermal decomposition, 3215-16 cyclometallation, 32:21 Organosulfur derivatives, of Group IV, decomposition of, 3222-23 51-92 nucleophilic addition, 32:21 Organosulfur ligands, rearrangements pyrolysis, 32:21 aminocarbene-thioether chelates, 3231 synthesis of, 3221 bridging ligands, 3227-28 dithiolenes, 3220 carbanionic complexes, 3229-30 fulvenes, 32:20 cyclic dithiocarbonate complexes, 3229 metallacycles cyclization, 3230 isomerization, 3225 deprotonation, 3227-32 photolysis, 32:24 dithioformate complexes, 3228 organothioformamide, 3217-18 dithiolate ligands, 3227 sulfur ylid, 3226 isocyanide-thioether complexes, 32:30 thiadiazoles methylthiovinyl tungsten complex, 3232 decomposition of, 3218 phenylkaminocarbene-thioether chelate, reactivity of, 3219 32:30 treatment of, 32:19 tungsten carbene complex, 32:31 thietes, 3220 Organotellurium compounds, reactions thioaldehydes, 32:14, 16-17 aryl complexes, 32:51 a-thioalkyl complexes, 3225-26 carbene complexes, 3251 thioaroylchlorides, 3212 carbynes, 3255 thiobenzophenone, 32 12 electrophiles thioesters, 3211 cycloaddition, 3280 Organotellurium compounds 232

olefins, 3280 structures, 35252-255 telluroacrylamide complex, 3272 tin as Lewis base, 35247-248 nucleophiles, telluroformaldehyde com- tin-transition coordination bond, plexes, 3292 35247-249 synthesis, telluroformaldehyde com- VSEPR model, 35250 plexes, 3296 X-ray crystal structure, 35248-250, 253 Organotellurium derivatives, of Group IV, iron compounds, 35247,252 581-83 magnesium compounds, 35251-252, 282 Organothallium chemistry, 1k147-202 nickel compounds, 35247,252 Organothallium compounds, 3158-159, palladium compounds, 35261-262 R23-25 platinum compounds, 39252 Organothallium(1) compounds, 11:148-155 singlet carbene analog structures, 35244 Organothallium(II1) compounds, tetravalent compounds containing C,N- 1k155-174 chelating ligand, 35260-271 conversion to aryl iodides, 1k1.58 tetravalent compounds containing C,Y- nitriles, 11:171 chelating ligand nitroso compounds, 1k170 Bailar twist, 35271 phenols, 11:159 basic fluxional processes, 35264 thiophenols, 11:172 Berry pseudorotation, 39275 Organotin amides chemical shift value, 35256-257 preparation, 3424-431 configuration inversion, mechanism, properties, 3431-433 35284 Organotin amines coordination geometry, 35257-258, nomenclature, 3416 260-261,263,268,281 preparation, 3416-419 diorganotin dihalides, 35279-286 properties, 3420-422,425-427 diptych derivatives, 35259-260, 268 reactions, 3423-424 EXSY spectroscopy, 35260 fluxional processes, 35264-268 aluminum compounds, 35282 geometrical isomers, 35285 bond angles, 35243-244 Lewis acidity, 35256 bond lengths, 35243 miscellaneous compounds, 35268-271 characteristics, 35243 monoanionic compounds, 35262-268 chromium compounds, 35247-248 monoorganotin halides, 35286-288 cobalt compounds, 35247-248,252 Mossbauer spectroscopy, 35256-257, coordination geometries, 35244-246 279, 287 divalent compounds containing C, Y-che- NMR spectroscopy, 35256-260.263- lating ligand 271,273,279,281-286 coalescence temperature, 35:254-255 octahedral compound arrangement, coordination geometry, 35250, 35279-281 252-253 schematic projection, 35267 diastereoisomeric structures, Sn-C bond reactivity, 35261-262 35250-251 Sn-chiral halides, 35265 heteroleptic compounds, 35252-254 stereochemical aspects, 35264-268 Karasch addition, 35247 Stille coupling reaction, 35261 Mossbauer spectroscopy, 35253 structural features, 35277 NMR spectra, 35250, 252-254 tin centers reactivity, 35255 configuration inversion, 35274-275 special features, 35247 transition states, 35275 stabilization by intramolecular coordi- trigonal bipyramidal compound ar- nation, 35249-255 rangement, 35281-286 233 Organotin heterocycles

triorganotin bromides, pentacoordi- hydrides, 9110 nate, 35266-268 hydroxides, 9115-116 triorganotin cations, pentacoordinate, inorganic salts, 9124 35269 ions, 9130-131 triorganotin chlorides miscellaneous derivatives, 9131-132 pentacoordinate, 35268 nitrogen compounds, 9123 syabilization, 35273 oxides, 9117 triorganotin halides, 35262-279 stannonic acids, 9118 hexacoordinate, 35270 stannoxanes, 9116-1 17 other, 35272-274 sulfur compounds, 9122-123 structural correlation, 35276-279 with tin-Main Group metal bonds, 9111 triptych derivatives, 35259-260, 268 with tin-tin bonds, 9111 X-ray structure, 35256-259,261-262, transition metal derivatives, 9124-126 265, 268-269,276-277, 280-281, Organotin compounds, "'"'Sn Mossbauer 286 spectroscopy, 921-134 tin bonds and valency, 35242-244 adsorption on surfaces, 9:85 tungsten compounds, 35248-250 compounds containing transition metals, zinc compounds, 35248-249 982 Organotin complexes determination of valency state, 980 in olefin metathesis, 16984, 288-289 diorganotin derivatives, 9:80 reaction with sulfur dioxide, 12:58 interactions in solution, 9:82 Organotin compounds, 447-63, 324-339, intramolecular interactions, 986 5137-167, 1463-69 labeling studies, 979 anionic species, 4326-327 molecular orbital parameters, 987 bond cleavage, 4327-332 nature of tin-transition metal bonds, 983 bonding, 5144-145 porphyrins, 982 catenation, &47-63 radiation damage, 984 configuration, 5139-144 reactions, 985 determination by IR spectroscopy, solid state structures, 988 5145 tin-oxygen heterocycles, 9:81 IR spectra, 5146-158 Organotin dihydrides radical species, 4326-327 addition to olefins, k.59-61 reaction with triorganostibine sulfides, with carboxylic acids, k82-84 14195-197 preparation of reduction, 4334 cyclic organotin compounds, k61 structural considerations, 5137-167 polymeric organotin compounds, 5-coordinate, 5140-142 k62-63 6-coordinate, 5142-143 reduction of aldehydes and ketones, k67 7-coordinate, 5144 of ketosteroids, k68-69 Organotin(I1) compounds, 19123-153 Organotin heterocycles bis(butadiene)cobalt complex, 19116-117 stannatranes and related systems, Organotin compounds, """Sn Mossbauer 33217-220 data, 9106-134 tin-Group 14 element bonds, 33172-185 alkoxides, 9115-1 16 homocyclic polytin compounds, alkyls and aryls, 9106-110 33183-185 carborane derivatives, 9126 rings containing other heteroatoms, carboxylates, 91 18-122 33181-182 divalent compounds, 9132-134 saturated heterocycles, 33172-177 halide complexes, 9126-130 unsaturated heterocycles, 33178-181 halides, 9111-114 tin-Group 15 element bonds, 33185-196 Organotin heterocycles 234

tin nitrogen heterocycles, 33187-191 organo derivatives, 9168 tin-phosphorus heterocycles, pseudohalides, 9166 33192- 196 Organotransition metal chemistry, tin-Group 16 element bonds, 33196-216 10:299-346 heterocycles, no additional heterodt- biological systems. 10339 oms, 33196-204 catalysis, 10331-336 tin-X-carbon heterocycles(X=O, S, Se, electronic structures, 10339 Te), 33204-216 fluorocarbon complexes, 10:315 tin-transition element bonds, 33220-226 general, 10300 iron, ruthenium, and osmium heterocy- historical and biographical, 10299 cles, 33220-224 Lewis base complexes, 10312 other transition elements containing ligand reactivity, 10337 heterocycles, 33224-226 literature, 1k447-468, 12379-404 Organotin hydrides metal-carbon u bonds, 10:313 addition to alkenes, k53-65 metal carbonyls, 10306-307, 309 to alkynes, kS6, 61-65 anionic, 10308 decomposition, k51-52 cationic, 10309 history, 1:47 metallocarboranes, 10325 IR spectra, k49-50 metallocenes, 10322 nomenclature, k47-48 metal-metal bonds, 10310-311 physical properties, k48-51 molecular nitrogen complexes, 10344 reaction with carboxylic acids, k82-84 organic synthesis, 10327 with organic compounds, k52-85 organoelement chemistry, 10303 reduction of acyl halides, k81-82 oxidative-addition reactions, 10336 of aldehydes and ketones, k66-70,82 a-complexes, 10317-321 of alkyl and aryl halides, k70-80 photochemistry, 10338 toxicity, k52 physical methods, 10340-342 Organotin intermediates, Ashe’s synthesis reaction kinetics and mechanisms, 10326 of alkali mctal boratabenzenes via, reviews, 1k456-468, l2384-386 25217 structural studies, 10342 Organotin-nitrogen compounds, 3413-439 techniques, 10302 complex compounds, 3413-416 Organotransition metal complexes heterocyclic nitrogen derivatives, optical activity, 18151-205 3433-439 0-8 rearrangements, 16:241-282 preparation, 3434 Organozinc compounds, 8173-174, 176, properties, 3435-438 12:83-119 structure, 3438-439 coupling reactions, 12112-114 nomenclature, 3416 Grignard-type addition reactions, Organotin radical anions, 15277 12:103-112 Organotin trihydrides, 38215 phosphine imines, 9286, 288 Organotitanium chemistry, 1050 as polymerization initiators, 12116-119 Organotitanium compounds reaction with arenes, 9171-172, 183 with acid halides, el12 divalent, 9175 with a-haloethers, 12:112-113 Organotitanium(II1) compounds, 9135-188 silanol derivatives, 9286 cyclopentadienyl derivatives, 9:152-171 Organyl(silyl)aminoorganyliminosilanes, acetylacetonate, 9164 39182 allyl, 9167 ORTEP drawings carbonate, 9:164 bis(ketene) complexes. 2841-43 hydride, 9168 kctenyl complexes, 28:60, 62 Osmium carbonyl clusters

ketenylidene complexes, 28:70-72 mixed-metal clusters, 18211-218, type I1 ketene complex, 2837-38 220-223 type I11 ketene complex, 2838 rhenium carbonylhydrides, 18232, type IV ketene complex, 2839 234-235 type V ketene complex, 2839-40 N-, 0-,S-, and Se-substituted carbene type VI ketene complex, 2839-41 complexes range of, 25142-146 type VIII vinylketene complexes, I3C NMR relaxation time tetracarbonyldi- 2840-42 methyl, 19261 Orthocyclization, of organopotassium com- tetracarbonyldihydride, reaction with plat- pound, 16182 inum(0) complexes, 18232 Orthometalated phosphine ligand com- trinuclear decacarbonyldihydnde, addi- plexes, 357-10 tion to metal-metal double bond, Orthometallation 18230-231 aromatic methyleneamines, 10157 Osmium, carbene complexes azo compounds, 10132 bonding models, 25123-125 in catalyzed hydrogenation by ruthenium carbene fragment, 25123 phosphine complex, 12324-325 charge distributions, 25124 manganesepentacarbonyl alkyls, coordination to metal, 25123-124 32185-187 geometries, 25124-125 rheniumpentacarbonyl alkyls, 37:207-208 substituent effects, 25124 of S-donor ligands, via phase transfer ca- reactivity patterns, 25125-129 talysis, 19207-208 effect of metal basicity, 25127-128 Osazones, 1:1 adducts with palladous chlo- reactions with nucleophiles, 25126-127 Osmium carbonyl ride, 13365 cations, 8143-144 OsCI(NO)(PPh&, reactions of nonhetero- Lewis base complexes, 3236-237 atom substituted Os, Ir, and Ru carbe- Osmium carbonyl clusters ne(alky1idene) complexes with, carbides, 2217-20, 28-32, 54 25156-1 57 effective radius of carbide, 2250 [OsCl(NO)(q2-E=CH2)(PPh.;)2] carbon dioxide, 22:132-134 oxidation, 43177 contraction reactions, 22194 synthesis, 43155 with hydroxide, 22195 Os3(C0)9Bi2,synthesis, 4295 decanuclear dianionic carbide, 2229-30 Os4(C0)12Bi2,structure and bonding fac- diprotonation, 2230 tors, 4247 reaction with iodine, 2230-32 Os3(CO)9(p-GeMe2)3,structure and bond- expansion reactions, 22:187, 191 ing, 42272 by auration, 22189 [osh(CO)~~(ph-P)]-,synthesis, 421 17 in Fischer-Tropsch reaction, 1275-77 Os,(CO)loNPh, synthesis, 4298 framework rearrangement, 22198-200 OsS(CO),,(POMe), synthesis, 421 12 halogen addition, 22184 [ Os( C0)2(PPh3)[ q2-E=CH2],synthesis, heptanuclear dihydride carbide, 2229 43154 hexanuclear alkyne carbide, 2229 Osmaborane clusters, 29201-202 high nuclearity metal, 14287 Osmate esters, fullerenes, 3669-71 IR studies, 14325 OS,M~(CO)ISPR,synthesis, 4285 structural data, 14288, 292 Osmium synthesis, 14325 dodecacarbonyl, activation toward substi- isocyanides, 22215, 231, 241 tution, 18232 of dodecacarbonyl, 22229 mediation of sulfur diimide cleavage, structures, 22247-248 36216 oxidative addition, 22181 Osmium carbonyl clusters 236

pentanuclear carbides, 2217-21 rnolccular rearrangements, 16320-323, anionic halide, 2218-19 328-335 hydrides, 22:19-21 hexanuclear, 16330-331 propadienylidene, 22121 hydride carbonyl, 16332-335 protonation, 22174 NMR data, 16320-323 reactions with nonrigid dodecacarbonyl, 16328 alkynes, 22185 mononuclear, 26:2 nucleophiles, 22176-177 nitrido, 2456, 64, 70, 78 reactions with, olefins, 12369-370 nitrosyl, 2442-46, 50-54, 56, 60-61 triangular facc-capping, 22181-183 carbides, 24:44, 46, 51-53 two-elcctron reduction, 22173 polynuclear, M:2 vinylidenes, 22118-122 trinuclear, 26:l-96 Osmium, carbyne complexes Osmium complexes bonding models, 25129-131 d'-alkylidene, synthesis carbene fragment, 25129-130 from carbyne complexes, 25159-160 charge, 25131 from hydroxy-, alkoxy-, and halo- heteroatomic substituents, 25130 methyl complexes, 25160-161 substituent effects, 25130-131 dRalkylidene, synthesis varying metal fragment, 25131 alkylidene formation mechanism, cationic d* complexes, 25184-185 25158-159 "C NMR spectroscopy, 25188 diazoalkane route, 25156 a-metalladiazoalkanes as precursors, reactions with 25183-184 O~Cl(NO)(PP,)~,25156-157 modification of other substrate complexes, existing carbyne complexes, 25184-186 251577158 existing ligands, 25182-184 allenyl, 3266. 81 oxidation of metal by anionic hydride iodine, 25186 spectroscopic properties, 275, 8, 23 oxygen, 25185 structural properties, 2218 reactions arene, 1366, 93 with acids, 2278 bimetallic, 32232, 235, 246 carbyne coupling, 2284-85 binuclear, 29237-238 with chalcogenides, 2294-95 carbonylation, 1M31 with metal complexes, 2R85-86 1,4-diaza- 1,3-butadiene photolysis, 2298 with chelated ligand, 21178-180 transformation to vinylidenes, 2296 substituent effects, 2k207 reactivity patterns, 25131-134 edge-bridged X-C,O-bonded alkylated electrophilic addition, 25133-134 clusters, 23:250 nucleophilic addition, 25131-133 electron-transfer reactions structure, 2755 carbonyl pentammine, 2327 synthesis, 25181-186, 2269 hexanuclear carbonyl, 24116-117 synthesis from dihalogenocarbcnes, osmocene, 2371 25182-183 tetranuclear hydride, 24117 vibrational spectroscopy, 25188-189 trinuclcar carbonyl, 24:112, 124 Osmium chloride, as catalyst, 38170 ethylene, "C NMR spectrum, 12:149-150 Osmium clusters, see also Triosmium face-bridged 2-C,O-bonded acyl clusters, clusters 23266 in CO reduction, 23290 formyls, 1267, 20:7, 9-11, 246 dinuclear, 262 protonation, 2022-23 237 Osmium

hexachloroosmic acid in hydrosilation, carbon-halogen bond, 25173-174 17:439-441 I3C NMR, 25175 hydridophosphines in catalyzed hydro- TR spectroscopy, 25175-176 genation, 12336-337 metal-carbon bond, 25173 iminooxosulfurance, 36:183-184 trans influence, 25175 main group Osmium, dihalocarbene complexes, syn- antimony and bismuth, 3k139-147 thesis tellurium, 3k165-167, 172 cation generation for CCIz with silver mononuclear salts, 25171 isocyanides, 22216, 222, 245 CClz complexes from reactions with vinylidenes, 2268, 100, 106-107 Hg(CClX)z, 25170-171 protonation, 2274 conversion of CClZcomplex to CFCl com- mononuclear, synthesis, 29235-237 plex, 25171 oxidative-addition reactions, R62, 72-74, modification of 79 a-dihalocarbene ligand containing com- phenylethynyl, 38125, 136 plex, 25171 photochemistry trihalomethyl derivatives, L,-CX3, carbonyl phosphine alkylidynes, 25169-170 M342 -342 Osmium, monohalocarbene complexes, syn- dicarbonylcyclopen tadienylhydroxy- thesis methyl, 24296-297 modification of tetracarbonyldimethyl, M300 carbyne complexes, 25172 polymetallic derivatives and, 29:229-235 a-dihaloalkyl derivatives, L,M-CX2R, redistribution reactions of carbonyls 25171-172 clusters, 23125 monohalocarbene ligand-containing hydrides, 23:117-118, 122 complex, 25172 with silyl ligands, 1k257 oxidative addition of [MezNCClZ]Cl, tetranuclear y-methylene, 20194 25172 trimethylenemethane Osmium, nonheteroatom-substituted car- NMR spectrum, 22292 bene (alkylidene) complexes reactions, with electrophiles, carbene ligand conformation, 25163 27:294-295 chalcoformaldehyde complex reactions, synthesis, 22285 25166 trinuclear, 29:237-238 electrophilic addition reactions, trinuclear dihydrido-y-methylene, 251 64- 166 20:171-173 gold adduct reactions, 25166 isomerism to methylhydride, halomethyl ligands as methylene precur- 20171 -1 72 sors, 25167 methylidyne formation, 20172 metal-carbon bond of, 25162-163 NMR spectra, 20209-210,212 nucleophilic addition reactions, Osmium, dihalocarbene and monohalocar- 25167-168 bene complexes nucleophilic addition to Os(=CH2) metal-carbon bond, 25173 Cl(NO)(PPh,),, 25167-168 metallacycle formation, 25179-180 reactions with halogens, 25167 migratory insertion reactions, 23180 reactivity, 25164-168 reactions with spectroscopic properties, 25163-164 electrophiles, 25180 structure, 25161-164 nucleophiles, 25176-179 sulfene complex reactions, 25166 structure synthesis carbene ligand orientation, 25175 d*-alkylidene complexes, 25156 Osmium

reactions with OsCI(NO)(PPhl)7, [Os3(p-S=CH2)(mz-S)(CO)9(PMe2Ph),syn- 25156-157 thesis, 43169 trans influence, 25163 Oxaazasilacyclobutanes, 39175, 181, 187 Osmium-platinum clusters Oxa-3-aza-2-sila-5-cyclohexene,39180 crystallographically characterized, 1,2-Oxaborolanes, alkyl exchange, 2:260 3k333-336 Oxacyclopenten-2-ylidene complexes, syn- exchange spectroscopy, 3k315-317 thesis, 4k225 fluxional behavior, 31:317-320 l-Oxa-2,6-diboracyclohexene, nickel com- high nuclearity, 3k358-363 plex, 18308-309 bicapped octahedral species, 3k358 1,2,3-0xadisiletanes, 39:256 bicapped tetrahedron species, Oxapentadicnyl complexes, of transition 3k358-360 metals, 26155-156 carbido species, 3k362-363 4-Oxa-l-phospha-2-silacyclobutane,39212 diplatinum bridged species, 3k360-361 Oxaphosphirane, synthesis with phosphaal- preparation from sulphido cluster. kenes, 41:s-6 3k361-362 1,3-Oxaphospholes, synthesis with phos- skeletal rarrangement, 3k360 phaalkynes, 4k43 skeletal structure, 3k361-362 Oxasclenostannolane, 39319 isomerization, 31:303-305 Oxathiastannolane, 39:319 synthesis, 31:303-305 Oxazolidinylidene complexes, 22284-286 tetranuclear, 3k351-358 Oxidation butterfly metal core, 3k351-358 alkanes, 15177-184 carbido species, 31:362-363 catalyzed by cobalt(III), 19182-184 via transition metal complexes, isomerism phosphine adduct. 15177-184 3k352-353 alkyl radicals by copper(T1) compounds, ligand loss, 3k353 12.310-312 preparation, 3k351. 355, 357 disilenes, 39262-266 reaction, 3k354. 356 germylenes, 44A52-153 spiked triangular core, 3k355,357-358 hydrocarbons by oxygen, 15149 thermal behavior, 3k352 reactions, alkanes, 38169-170 two-electron donor ligand reaction, reactions, organocopper compounds, 3k352 12254-259 trinuclear, 3k350-351 in synthesis of organometallic 0x0 com- bridging carbonyl, 3k350-351 pounds, 28:342-347 diplatinum, 3k351 Oxidation-rcduction potentials, substituted preparation, 3k350 ferrocenes, 1098-101 Osmium-substituted carbene complexes Oxidation-reduction studies, n-ollyl com- rcactivity plexes, &lo7 carbene ligand rearrangement, 25155 Oxidative addition nucleophilic substitution reactions at acetic acid to butadiene, 12181 Ca, 25149-153 alkyl halides to Group VIIl metal com- oxidative addition reactions, plexes, 14381-388 25154-155 mechanism, 14382-388 spectroscopic properties, 25149 aryl halides to nickel phosphines, structure, 25146-148 23118-119 synthesis, 25135-146 B-H-B bridges, 14183 Osmiumtetracarbonyl, 32232 B-H bonds, 14180-182 Osmocene, 8271 in carbonylation [Os~(p?-SCH2)(CO),,],synthesi, 43168 of methanol, 12259 239 Oxygen -cente red radical

via organonickel compounds, 17:225 in synthesis of metal heteronuclear clus- germanes to palladium complexes, 13288 ters, 29:255-256 hydrogen transition metal complexes, 254-90, in Fischer-Tropsch reaction, 1289-90 162-164 to osmium carbonyl clusters, acetylenes, 265-67 12369-370 definition, 254 photoassisted to iridium complex, dimethyl sulfoxide, 2103 12378-379 factors affecting, 255-58 to rhodium in catalytic hydrogenation, kinetic and mechanistic studies, 254- 12322 55, 58-59, 164 to thiolato-bridged indium complex, oxygen, 263-65 12372 perfluoroalkyl iodides, 7531, 83 in hydrosilation, 12412 as source of a-bonded alkyls (aryls), and ionization potential, 12196 2162-164 and metal-catalyzed organosilane redistri- stereochemistry 59-63 bution, 19247-251 five-coordinate complexes, 7:62 methyl iodide to platinum, 12259 four-coordinate complexes, 759 one-electron-transfer mechanisms, 2317 Oxides, of mixed alkali metal compounds, iron carbonyl phosphines, 2325-26 22235 nickel(I1) phosphines, 2333-34 Oxide-supported triosmium clusters, as cata- organic halides to palladium phosphine lysts, 2663-64 complexes, 13387-388 Oxidizing agents, for preparation of organo- to organogold(I), 2041, 61, 64-66, 84, 87 metallic 0x0 compounds, 28343-345 in platinum(I1)-catalyzed H--D exchange, Oxiranes, from arsonium ylides, 20146-147 15170 0x0 acetylene compounds, 28:351-356 in preparation of supported transition 0x0 alkylidene compounds, 28351-356 metal catalysts, 15205 0x0 alkylidyne compounds, 28351-356 protonic acids to platinum complexes, Oxoberyllium alkyls, 9230 13279-283 0x0 carbonyl compounds, 28:351-356 silanes to bis-ethylene platinum com- 0x0 olefin compounds, 28351-356 plexes, 12412-413 0x0-n-ally1 complexes, 13377 to zero-valent nickel 0x0 reaction, 4255 acyl halides, 12222 0x0 synthesis, see Hydroformylation Bronsted acids, 12113, 118 Oxygen metallacycle formation, 17:198-I 99 addition to metal complexes, 263-65 organic halides, 12208 adduct with iridium carbonyl-phosphine in pseudo-Grignard reactions, 17:217 complex, 3245-246 silyl compounds, 12243 effect on alkali metal GIC catalytic activ- Oxidative addition reactions, 10336 ity, 28108-109 computer representation, 26:176, 182-183 reaction with feasibility matrix, 26182 digermenes, 44A37-138 geometry, 26182 germenes, a124 to isocyanide complexes of nickel and pal- silenes, 39138 ladium. 1k31 sensitivity, substituent effects in metallo- N-, 0-,S-, and Se-substituted Ru, Os, cenes, 40130-132 and Ir carbene complexes, terphenyl derivatives, 4450, 52 25154-1 55 Oxygen-centered radical, reactions organoplatinum complexes, 22114, 116, with Ge hydrides, M88, 90 120-121, 124-125, 128-130, 159-160 with Si hydrides, 44233, 85 organosilicon compounds, 1k268-270 with Sn hydrides, MY9, 101 Oxymercuration 240

Oxymercuration, of alkylidynetricobaltnona- p-cyclopentadienyl-p-halide, 19176 carbonyls, 14125 p-cyclopentadienyl-p-thiolate,19166 3-Oxy-l-metalla-1,2,3-butatrienes,synthesis, electron-deficient bis(phosphine), 19159, 4k215-216 161 Oxyplumbation reactions, 2301 mixed alkali metal compounds, 22256 a-Oxy radical, reaction with Sn hydrides, mixed-metal clusters, 18211. 220. 226 U98 Palladium catalyzed rcactions, butadiene, Oxythallation reactions, 11:174-202 12141-193 cyclopropanes, 1k182 catalyst recovery, 12148 olefins, 1k160, 174-179, 186 catalytic species, 12146-148 effect of acetate, 11:180 with COz, 12178-179 mechanism, 11:177, 180-181 cocyclization steroidal olefins, 1k185 with aldehydes, 12146 with C=N bonds, 12146 comparison with nickel catalysis, P 12143-146 Palladium, 3864, 72-73 dimerization, 12145, 148-150 p-acetates, 19:164- 166 in formic acid, 17:149 allyls, NMR spectra, 19279-281 to octadienes, 12149 ~-allyls-p-carboxylate,19162-163 to 1,3,7-octatriene. 12148-149 p-allyls-p-halide, 19:161-162, 165 in presence of COz, 12149-150 p-arene, 19155, 178-179 lack of cyclooligomerization, 12145 bis-p-allyls, 19160, 164 telomerization, 12151-168 bis-pcyclopentadienyl, 19165-166 with active methylene compounds, bis-pditertiary phosphine, 19178 12159-162 reaction with electrophiles, 19178 with active methyne compounds, p-cyclopentadienyl 12159-162 bonding, 19167-169 with alcohols, 1732-155 fluxionality, 19168 ally1 intermediates, 12152-153 mechanism of formation, 19170-174 with amines, 17:158-159 p-cyclopentadienyl-p-allyl,19156-164, with ammonia, 12157-158 170-174 carbonylation, 12165-167 allene elimination reactions, with carboxylic acids, 12155-157 19161-162 with enamines, 1R1.59 heteronuclear platinum complex, formation of substituted octadienes, 19160 12151-1 68 kinetic studies, 19170-174 with oximes, 12167 mechanism of formation, 19156-159 with phenols, 12152 from monomeric allylcyclopentadienyl with phenylhydrazones, 12167 complexes, 19:172-173 with silicon compounds, 17:155, phosphorus-donor derivatives, 162-165 19:156-165 with water, 12151-152 reaction with trimerization. 12150 electrophiles, 19174 Palladium chloride, in oxidation of ethylene nucleophiles, 19176 to acetaldehyde, 5321-352 synthesis, 19157-162 complexes in solution, 5323-324, p-cyclopentadienyl-p-carboxylate,19166, 328-329 176 effect of copper(I1) salts, 5339-343 ~'-cyclopentadienyl-~5-cyclopentadienyl Palladium chloride-TPPMS complex, 38175 phosphine derivatives, 19165-166 Palladium clusters, 3553, 108, 121 241 Palladium(0) catalyzed reactions

Palladium complexes synthesis, 22285 acyclic pentadienyl, 26:153 tropyne, synthesis and reactivity, 42:182 alkyl, 38:108 vinylidenes, 2294-95 alkynyl, 3887, 89, 108, 111 ylides, 20:152-153 anionic hydride, spectroscopic properties. zero-valent addition 225 metal carbenes and carbynes, bimetallic, 32229, 237, 243, 260, 283, 285, 18:231-232 287, 297 unsaturated metal-metal bonds, boranes, 2k64-65 18231-232 carbonyl, 3250-251 Palladium complexes, catalysis electron-transfer reactions codimerization of ethylene and butadi- pacetylenecylopentadienyl. M110 ene, 17:315-316 allyls, 2337-38 hydrogenation, 12331 cyclopentadienyls, 2362-63 hydrosilation of conjugated dienes, mixed-metal clusters, 24111-1 12 12441-442 phosphines, 2332 isoprene dimerization, 12168, 172-176 germathiones, 2k257 head-to-tail, 12168 main group tellurium, 3k173 isomer distribution, 17:168-169 via metal atom synthesis, 15100 reductive, 17:172-173 dibenzylideneactone, l572 telomerization, 17:168-172 insertion reactions, 15101-103 asymmetic, 12170 k-methylenes, 20248 with methanol, 12169-170 olefin, $324-326 Palladium compounds structure, 5326-328 carbonylation, 1k137-138 perfluorobicyclo[3.3.O]octadienyl, 3k241 reactions with isocyanides, 1k31-35 phenylethynyl, 38:128, 132, 135, 137-138 Palladium-C6X5 bonds, isocyanide insertion photochemistry reactions into, 28:267-277 alkylbis(phosphine) halides, 24320-321 Palladium, 1,4-diaza-t ,3-butadiene com- dialkylbis(phosph1ne) compounds, plexes 24318-320 bridged compounds, 2k165-167 platinum cluster with chelate ligand, 2k169, 189 bimetallic, 3k376 fluxionality, 21:159, 162-164 different metal, 31:377-379 metal-nitrogen bond strength, 2k164-165 reactions with carbon dioxide with monodentate ligand, 2k157-165 allyls, 22159, 161-162 X-ray structure, 2k158, 160-161 catalyzed ethyl formate formation, Palladium dichloride, 26:153 22157 Palladium-graphite, 28120-121 insertion into metal carbon bonds, Palladium, isocyanide complexes, 1k74-75, 22146- 147 22237-238,251 reactions with methylcobalamin, 20319 addition of alcohols and amines, 11:46 redistribution reactions, 23:96 binuclear species, 22250-251, 253-254, alkyls, 23119-121, 124-125 262 allyls, 23103-105 homoleptic clusters, 22223-224 cyclobutadiene derivatives, 23111-112 linear trinuclear species, 22224, 266 phosphine halides, 23108-109, 112, reaction with amines, 22:291 114-116 triangular cluster, 22223, 249-250 square-planar, third-order nonlinear op- Palladium(0) catalyzed reactions tics, 43275, 377-378 addition of hydrogen cyanide to olefins, trimethylenemethane 13423 role in organic synthesis, 22301-307 hydrosilylation, 13423 Palladium(0) catalyzed reactions 242

of quinones, 13432-433 nature of products, 13397 Palladium(0) complexes, 38182 in alcohol in presence of carbon monox- acetylenes, 1337.5 ide, 13399-402 addition reactions, 13440 of cyclic olefins, 13401-402 protonation, 13301-302 nature of products, 13399 carbonyls, 13367-368 stereochemistry of butene carbonyla- olefins, 13370-374 tion, 13400-401 stability of phosphine derivatives, of allylic alcohols to acrolein, 13385 13375 mechanism, 13386 susceptibility to nucleophiles, 13370 in aqueous solution, 13378-388 Palladium(1) complexes, 13369 to form acetaldehyde, 13378-385 carbonyls, 13367 of allylic compounds, 13:385-386 by cyclization of diphenylacetylene, to form ketones, 13388 13439 cyclopropanes, 13387-388 reactions with nitric oxide, 13369 ethylene Palladium(1) complexes, binuclear metal to acetaIdehyde, 13370 containing bridging ligands, 28280-287 in acetic acid, 13388-397 without bridging ligand, 28287-288 effect of cupric chloride addition, Palladium(II), addition with nucleophiles to 13379,384-385 unsaturated substrates, stereochemistry mechanism, 13378-385 addition to acetylenes, 13443 to vinyl acetate, 13388-389 addition to strained diolefins, 13442 olefins, 16:253-254 effect of nucleophiles, 13:442 reactions with carbon-carbon bond forma- electronic effects, 13:442 tion, 13:402-413 hydroxypalladation, 13441 aliphatics, 13409-412 in Wacker process, 13:443-444 aromatics, 13402-409 Palladium(II), catalysts, 38170-171, 182 arylation of enol esters, 13404 Palladium(II), (~'-allyl) complexes, organo- coupling of organic halides, 13409 metallic chemistry, 342-7 coupling of wsubstituted styrenes, intermolecular coordination systems, 13409 34.39-55 formation of aromatic chlorides, 13403 nitrogen donor ligands, 342-38 formation of cinnamic acids, 13403 palladium(1V) complexes, 3426-38 mechanism of vinylic coupling, poly(pyrazo1-1-yl) alkane ligands, 342-38 13411-412 poly(pyrazo1-1-yl) borate ligands, M2-38 preparation of styrene, 13402 square planar(I1) complexes, 347-23 Palladium(I1) catalyzed reactions, Palladium(I1) carbonyls, cationic, synthesis, 13~363-452 28233-234 acetylenes, 13434-441 Palladium(I1) catalyzed oxidations, formation of palladiacyclopentadienes, 13378-412 13437 in acetic acid oligornerization to cyclic olefins, with added oxidant, 13394-397 13434-436 of cyclohexene, 13390 diolefins, 13425-433 kinetic studies, 13:391-394 formation of stable palladium-carbon production of saturated esters, u-bonds, 1342.5-428 13394-395 formation of stable palladium(I1) ad- of straight chain olefins, 13389-391 ducts, 13421-422 in alcohol in absence of carbon monox- via addition to carbon-carbon bonds, ide, 13397-399 13422 mechanism, 13397-398 via oxypalladation, 13421 243 Pentaalkylstiboranes

hydrogenation of polyunsaturated esters, cobalt-alkyne complexes in organic syn- 13433 thesis, 41:117 hydrosilylation of olefins, 13423 synthesis of cyclopentenone derivatives, isomerization of olefins, 13420-421 4k210 mechanism, 13420-421 p-block elements, terphenyl derivatives nonoxidative dimerization of olefins, A1 compounds, U23-25 13425 As compounds, a45-47 olefin exchange reactions, 13412-419 B compounds, U19-23 unconjugated dienes, 13432-433 Bi compounds, U47-50 Palladium(I1) complexes, 28220 C compounds, U31-32 acetates, 13366-367, 374 In compounds, M30 acetylenes, 13374 Ga compounds, U25-27, 29 a-allyls, 13375-378 Ge compounds, 44:33-39 from ally1 halides and palladous chlo- Group 17 derivatives, U56-58 ride, 13375-376 Group 13 elements, 418-19 by carbene insertion, 13377 N compounds, U39-41 cationic species, 13378 0 compounds, 4450, 52 chiral complexes, 13378 Pb compounds, a33-39 from divinylcarbinols, 11377 P compounds, U41-45 carbomethoxy species, 13367 Sb compounds, U47 carbonyls, 13367-368 S compounds, 4452-55 diene u-adducts, 13428-433 Se compounds, U55-56 carbonylation, 13429 Si compounds, U32-33 exchange reactions, 13430 Sn compounds, U33-39 oxidation, 13430-432 Te compounds, 4456 rearrangement, 13:428 TI compounds, 44:30 diolefins, 13371, 425-427 PCO~(CO)~,synthesis, 4276 reactions, 13425-427 [PdCl2{7'-SC7H&], synthesis, 43145 direct arylation with Grignard and organ- Pdg(PPh3)8Sb6,synthesis, 4282 olithium reagents, 28:221-226 Pentaalkylphosphoranes, 14214-224 hydrides, 13368-369 cyclic species, 14215 olefins, 13370-374 via insertion of ylides into silacyclobu- dimeric species, 13372-374 tanes, 14215 importance of u-donation, 13371-372 as intermediates, 14217-224 vinyl ethers, 13:371 in ylide cleavage of 1,3-disilacyclobu- perhalophenyl tanes, 14218-219 with one C6X5group bonded to each in ylide cleavage of monosilacyclobu- metal center, 28:229-240 tanes, 14219-224 with two C6X,groups bonded to each polycyclic species. 14215-217 metal center, 28240-255 spectral studies, 14:216 with three C,Xs groups, 28256-266 synthesis, 14216 Palladium(1V) complexes, 28278-279 thermal stability, 14216-217 [2.2]Paracyclophane-l-yne,transition metal Pentaalkylstiboranes, 14232-236 complexes, 42197-199 NMR spectra, 14234 Paramagnetism, of 1,3-ditungstacyclobuta- reactions, 14234-236 diene, 26:104 with Bronsted acids, 14:235 [P(AuPPh,)#+, structure and bonding fac- with Lewis acids, 14235 tors, 42:40 with oxidizing agents, 14235-236 [PAu5(PPh3),][BF,J3, synthesis, 4283 synthesis, 14232-233 Pauson-Khand reaction of alkenyl species, 14233 Pentaal kylstiboranes 244

of methyl compound, 14:232 Pentacarbonylmetallate(3-) of vanadium via organometallics, 14232-233 aminepentacarbonylvanadate(1-) anion of trimethylsilylmethyls, 14233 reaction, 3k25-26 thcrmal dccomposition, 14233-234 synthesis, 3k25-26 vibrational spectra, 14234 characterization Pcntaaryl bismuth compounds, see Bismuth, trirubidium, cesium, and potassium pentaaryl compounds salt, 3k16 Pcntaarylphosphoranes, 14214 "V, I3C,and 'H NMR study, 3k20-23 Pentabenzylcyclopentadiene, synthesis of, with main group electrophile 33303-304 mechanism, 3k24 Pentabenzylcyclopentadienylindium,33337 reaction, 3k24 Penta benzylcyclopentadienylpotassium- protonation tris(tetrahydrofuran), 33337 'H and "V NMR study, 3k20-23 Pentabenzylcyclopentadienylthallium, isolation and identification, 3k20 33334-337 salt bonding, 3M7 2k80 Pentaboraferrocene, synthesis, 3k15-18 structure, 21:72 thermal stability, 3k16-17 Pentaboranc complexes with triphenylphosphine gold(1) chloride copper-iron compound, 2k91 eight-coordinate complex, 3k24 isomerism, 2k94-95 structure, 3k24, 26 valence tautomerism, 21:103 vanadium carbonyl comparison, 3k24 Pentaborane(9) derivatives, 3297-300 Pentacarbonylrhenate, 32234, 245 Pcntaborane(l1) derivatives, 3299, 301-302 Pentacarbonylrhenium ethynide, 32247 Pentacarbonylmanganate(4) and hexacarbo- Pentacarbonyl( tetrafluoroborato)rhenium, nylmanganese(1) coupling, 3373-74 37:247 Pentacarbonylmetallate(3-) of niobium and tantalum Pentacarbonyltungsten s-pyridine com- amine derivative plexes, third-order nonlinear optics, n-acceptor ligand reaction, 3k31 43375-376 preparation, 3k30 Pentachlorophenyl derivatives, 28292-293 structure, 3k30 Pentacovalent configuration, of polysilanes, characterization k109, 137 elemental. 3k19 Pentacyanocobaltate(II), as hydrogenation IR spectra, 3k18 catalyst, 16264-265 tricesium salt, 3M9-20 for butadiene, 16:264-265 hydride derivative Pentacyanocobaltate(III), 1k333 'H, "'Nb, and "C NMR spectra, cobalt-carbon bond cleavage, 1k408-410 3k27-29 formation of nitriles, 11:428 hydride transfer agent, 3k29 homogeneous hydrogenation with, 1k433 metal carbonyl reaction, 3k29 organic derivatives, 1k381-383 preparation, 3k27 reaction with sulfur dioxide, 1k430 triphenylphosphine gold complex, synthesis, 1k394-396 3k30 (E)-1,3-Pentadiene, in photochemical reac- isocyanide derivative, 3k31 tions with carbonyl complexes stability, 3128-19 of chromium, 26:298,325-327,329 synthesis with decacarbonyldimanganese, reduction hexacarbonyl( 1-) anion, 26:354-357 3k18 of molybdenum, 26:299,338-339,345, tricesium salt, 3k19-20 347 trisodium salt, 3k20 of tungsten, 26341, 351 245 Pentarnethylcyclopentadienylboranes

(Z)-lS-Pentadiene, in photochemical reac- qs-Pentadienyltricarbonylmolybdenum tions of metal carbonyl complexes anion, 26151-152 of chromium, 26316 bonding parameters, %152 with decacarbonyldimanganese, reaction with iodomethane, 26151 26354-355 Pentadienyltricarbonylrhenium,26149-150 1,4-Pentadiene, 26127 7'-Pentadienyl(triethy1phosphine) Pentadienylboranes, 26133-134 molybdenum, 26138 Pentadienyl cation analogs, 39:34-35 (Pentaethylacetophenone)Cr(C0)3, Pentadienyl complexes, theoretical studies, 34303-306 1530-31 Pentafluorophenylcopper, 245 Pentadienylmetal complexes, see Acyclic Pentafluorophenyl derivatives, 28288-291 pentadienylmetal complexes boron, k145, 150,158-159 7'-Pentadienylmetal complexes, 26143 lead, k150 $-Pentadienylmetal complexes, 26141-143, lithium, W49-150, 158 153-154 magnesium, k150, 204 structures, 26142 mercury, 1:150,204-205 synthesis, 26153-1 54 tin, k150, 153, 159, 166-167, 169, 172 Pentadienylsilanes, as organic reagents, transition metals, k150, 178-188, 26134-135 190-195 Pentadienylstannanes, as organic reagents, Pentafulvenes, reactions with tricarbonyl(- 26134-135 coordinated diene) chromium com- Pentadienyltetracarbonylmanganese com- plexes, 26333-335 plexes, 26150 Pentahalophenyl metal compounds, IR spec- q5-Pentadienyl-transition metal complexes, tra, 28288-293 bonding, 26156-158 Pentahydrodiborate anion 7'-Pentadienyltricarbonyliron cations, comparison with hexaborane, 2k75 26143-147 ethylene analogy, 2k72-75 alcohol derivatives, 26144-146 complexation, 2k73 protonation, 26.1 44- 145 MO calculations, 2k73-75 1-alkyl derivatives, 26147 Pentakis(methylthio)cyclopentadiene, syn- dinitrobenzoate esters, 26145 thesis, 33306, 309 reactions with nucleophiles, 26146-147 Pentalene complexes alkoxybenzenes, a146 nonrigidity, 16340-341 hydride donors, 26147 ruthenium, 15117 methylamine, 26146 Penta(methoxycarbonyl)cyclopentadiene, trimethylamine, 26147 synthesis, 33309 trimethylphosphite, 26:147 Pentamethylarsorane, 14229-231 triphenylarsine, 26147 NMR spectra, 14230 triphenylphosphine, 26147 reactions, 14230 weak bases, 26146 structure, 14230 stereoisomers, 26144-145 synthesis, 14229-230 synthesis, 26143-147 thermal decomposition, 14231 Pentadienyltricarbonylmanganesecom- Pentamethylcyclopentadienyl arene ruthe- plexes, 26149-150 nium complexes, 29:190 reactions Pentamethylcyclopentadienylboranes, with carbon monoxide, 26150 26238-239 carbon monoxide dissociation, 26150 I'B NMR chemical shifts, 26:239 with phosphines, 26150 reactions, 26238 trimethylphosphine adduct, 26150 structures, 26238 Pentamethylcyclopentadienylgermanium chloride 246

Pentamethylcyclopentadienylgermanium cleavage rates, 34189 chloride. 26262-263 complexation, thermodynamic parame- calculatcd orbital energies, 26263 ters of, M187 chloride abstraction, 26265 ionization potentials, 34184, 189 structurc, 26260 kinetic examination, 34189 synthesis, 26262 kinetic parameters, halogens, 34191 vertical ionization energies, 26263 photoelectron spectra, 34183-184 Pentamethyldisiloxane, catalyzed redistribu- rate parameters, 34190 tion, 19:238-240,243 spectral characteristics, 34188 l-Pentamethyldisilyl-4-trimethylsilybenzene, halogens, 34:191 photolysis, 39109 tetracyanoethylene, interaction with, Pentaphenylborole, 39:363, 380 34154- 188 Pcntaphenylcyclopentadiene Peralkylsilyl anions, 3811-12 stabilization, 33319-323 Peraryl cyclohexastannanes, 38218 synthesis, 33301 -302 Peraryl distannanes, 38:194-197,200 Pentaphenylgermole, 2k243 Perethylcyclopentadienes, synthesis, Pentaphosphadeltacyclanes, synthesis with 33306-308 phosphaalkynes, 4k58 Periluoralkylnickel carbonyl anion, 2250 Pentastannancs, 38208-209, 21 1 s-Perfluorally transition complex, 2356 Pentastanna[l.l .l]propellane, 3R20 Perfluoroacyl, transition metal derivatives, Pentazenes, derivatives of Group IV ele- 1:186,189-195 ments, 24246-247 Perfluoroacyl halides, k178-180 Pentenes, hydroformylation, 6132-135 Perfluoroacyl metal compounds, 331 Peptide synthesis, via carbene complexes, 14:ll-12 Perfluoroalkyl complexes, alkyl comparison bond length, 31:186 Peralkyl cyclopolystannanes, 38:218 Pcralkyl distannanes, 38195, 197-198, 202 bond strength, 3k185 Peralkyl polymctals, charge transfer com- carbonyl insertion, 3k187-188 plexes Fenske-Hall calculation, 31:186-187 charge transfer frequencies, 34195 a or p elimination, 31:188 charge transfer spectra, 34194, 197 reactivity, 31:187-188 halogens, 34197 thermodynamic stability, 3k185 ionization potentials, N197 Perfluoroalkylcopper compounds, prepara- kinetic studies, N195-196 tion, l2226-228 molar extinction coefficients, 34:198 Perfluoroalkyl derivatives oxidation rate correlations, 34198 aluminum, k160 stability constants, 34198 boron, k145, 154-156 tetracyanoethylene, M194-198 cadmium, k201 transition metal fluorides, 34197 germanium, k165-166 visible absorption spectra, changes in, Grignard reagents, k1.51 34196 iodides, k144-145, 150-151, 180-181, Peralkylpolysilancs, charge transfer com- 184-186 plexes iron, k216 absorption spectra, 34:184, 186 lead, k166, 174, 203 a-acceptors, 34183-188 lithium, k144-147, 168 cr-acceptors, 34188-191 manganese, k186-187,191, 206, 214-215 Arrhenius equation parameters, halo- mercury, 1:144. 153, 201-205 gens, 34191 rhenium, k214-216 Benesi-Hildebrand method, 34187 silicon, k145, 161 charge transfer energies, 34185, 190 tin, k154, 162, 165-171, 180, 203 247

transition metals, k145, 178-195, 203, metallacyclopentane, 3k192 214-21.5 pyramidalization of ligated carbon, zinc, k145, 147,200-201 3k192 Perfluoroalkyl iodides, in oxidative addition Perfluoroolefins, reaction with iron carbon- reactions, %81, 83 yls, k27-28 Perfluoroalkyl metal compounds, 326-29, Perfluoro-r-allylic metal complex, k196 31, 35 Perfluorophenyl-metal compounds, 343 Perfluoroalkyl metal nitrosyls, 7:229 Perfluoropropenyl manganese carbonyl, Perfluoroallyl chloride, 347 347 reaction with alkali metal carbonyl met- Perfluoropropyltin compounds, k147 allates, k183-184 Perfluorovinyl derivatives Perfluoroallylic complexes boron, M56-159, 170 anionic species, 3k196 Grignard reagents, k1.52-153 $-pentafluoroallyl compound, lithium, k148-149, 164-165 3k194-196 magnesium, k149 isomerization, 3k196 silicon, k164-165 MO calculation, 3k196-197 tin, 1:148, 152, 156-157, 164- 167, Perfluorobenzene complexes 172-173 T2-bonded, 3k199 Perfluorovinyl-metal compounds, k43-45 $-bonded, 31:199 Perfluorovinyl-metal derivatives u-bonded, 31:199 infrared, k213-214 platinum Dewar valence isomer, liquid film spectra, k213 3k199-200 NMR of As, B, Ge, Hg, Si, Sn, k211-212 Perfluorobicyclo[3.3.O]octadienediyl ligand Perhaloaryl platinum complexes, anionic, cobalt, 3k221-222 basic behavior, 28.258-259 nickel, 3k242-245 Perhalophenyl complexes of palladium(I1) palladium, 3k241 and platinum(II), with one C6X5group Perfluorocarbon-metal derivatives, IR spec- bonded to each metal center tra, k212, 214-216 cationic, 28232-236 Perfluoro-1,3-diene complex neutral, 28229-232 bonding, 3k197 single-bridged polynuclear, 28237-240 7'-pentafluorocyclopentadienyl, 3k198 Peri ring, conjugate addition of Grignard, hydrocarbon comparison, 31:197 k227 oxidative addition, 3k198 Perisopropylcyclopentadienes, synthesis, Perfluoroethyltin compounds, 1:152 3k306-307 Perfluoromethylmagnesium iodide. Permethylpentastannane 21.5, 38216 k150-151 Peroxide, decarboxylation initiated by, Perfluoronorbornadiene, 32230 25268-269 Perfluoro-n-propylmagnesium iodide, k151 Perphenylated cyclosilanes Perfluoroolefin complexes decaphenylcyclopentasilane, k125-130 cyclopropene ring opening, 3k193-194 dodecaphenylcyclohexasilane, k130-132 irreversible, 3k194 octaphenylcyclotetrasilane, M17-125 stereoselectivity, 31:194 structural studies, k94-102 dynamic behavior Perstanna-[n]-prismanes, 38234, 236-237, bonding, 3k193 239 cyclization, 3k193 Perstanna[l.l.l] propellanes, 38235-236 NMR study, 3k192-193 Perturbation of molecular orbital method, rotation activation barrier, 3M92-193 34175 structure and bonding, 3k191-192 Peterson-type reactions, germene, a116 hydrocarbon comparison, 3k191-192 P,(Fpll, synthesis, 42:88 Pharmacology 248

Pharmacology, of silicon compounds, in stoichiometric organic synthesis, 18276-281 19185-189 Phase-transfer catalysis, hydrogenation, substituted ferrocene synthesis, 19207 17:368 [PhCH2NMe1][ Se6Fe6(CO) ,a], synthesis and Phase-transfer catalysis in organometallic structure, 41:263-264 chcmistv, 19183-211 a-Phellandrene, 29191 alcohol dehydrogenation, 19:199 Phenanthrene, antimony trichloride adduct, alkylation of arylaceticesterchromium car- 26..284 bonyl, 19208 Phenolate derivatives. terphenyl-substituted alkylidyne nonacarbonyltricobalt forma- derivatives, 44:3 tion, 19209 Phenolic ketones, conjugate addition of allyl alcohol isomerization, 19199-200 Grignard, k235-237 ally1 complex synthesis, 19204-206 tautomerism, k235-237 r benzyl complex formation, 19206 Phenols, from arylthallium trifluoroacetates, carbcne insertion into dieneirontricarbo- 1k169 nyls, 19206-207 Phenoxide anions, shape of HOMO, carbonyl substitution, 19201-203 20298-299 and cobalt tetracarbonyl anion, Phenylacetylene reactions 19190-192 addition to germenes and digermenes, in allyl complex synthesis, 19:190-191 39299-300, 320 in dehalogenation of activated halides, with phosphasilenes, 39212 19191-192 with tin doubly bonded compounds, 39315 dicobaltoctacarbonyl as carbonylation cat- alyst, 19190-192 Phenylacetylene reactions, digermenes, &135-136 acyl intermediates, 19192-195 9-Phenyl-9-arsafluorene, structure, 4:206 of alkynes, 19195 Phenylarsazine chloride, see lO-Chloro-5,lO- of enones from polyenes and methyl io- dihydrophenarsazine dide, 19195 1-Phenylarsole, synthesis, 39:328, 330 of halides to carboxylic acids, 19192 Phenylation reactions, 106 of quaternary ammonium salts, Phenylazocarboranes, methyl rheniumpenta- 19196-197 carbonyl reaction, 37:212 halide exchange rcactions, 19203-204 Phenylbismuthine, 39:327-328 nickcl tetracarbonyl as catalyst Phenyl(bis(2,3,4-triphenyl-l- carbonylation of allyl halides, 19197 naphthyl)borane, 39381 cyanation of aromatic halides, 1-Phenylboratabenzene anion, 39384 19200-201 Phenyl bridge, in mixed metal organics, ortho-metalation of sulfur donors, 2R212-215 19:207-208 Phenylcarbene ligand palladium complex catalysis conformation, 25163 carbonylation of halides, 19197 trans influence, 25163 cyanation of vinyl halides, 19200 Phenylcinnamaldchydc, reaction with si- phenylation of a,P-unsaturated ke- lenes. 39125 tones, 19201 Phenyl compounds, 'jC chemical shifts, pentacyanocobalthydridc anoin, catalyzed 12:140-141, 170 reductions, 19197-199 l-Phenyl-4,5-dihydroborepin,39386 of conjugated dienes, 19197-198 l-Phcnyl-2,S-dimethylarsole,39327, 333 of @unsaturated ketones. 19198-199 l-Phenyl-2,5-dimethylbismole,39327-328 rhodium complex-catalyzed hydrogena- l-Phenyl-7,8-disilabicyclo[2.2.2]octa-2,5- tion, 19197 dienes, 3&38 249 Phosphasilenes (silylidenephosphanes) o-Phenylenebis(dimethylarsine),see Di- Phenyllithium, diheteroferrocene synthesis arsine with, 39326-327 o-Phenylenediarsine oxychloride, structure, Phenyl-metal compounds, 341-43 4:205 Phenylnonamethylcyclopentasilane, Phenylethynyl-chromium complexes, 38122, 38:37-38 135 Phenyloligosilanes, action of lithium metal, Phenylethynyl-cobalt complexes, 38125- 3831 126, 137 3-Phenylpentadienyltricarbonylchrornium Phenylethynyl-gold complexes, 3889, 108, anion, 26151 111-113, 119 Phenyl rheniumpentacarbonyl, synthesis, Phenylethynyl-hafnium complexes, 38122, 37:175 135-136 Phenylsilyl anions, structure, 387-9 Phenylethynyl-iridium complexes, 38127- Phenylsilyl group, 38:41 128, 132,137-138 (Phenylsilyl) lithium, 388, 28 Phenylethynyl-iron complexes, 38123-124, Phenylstibine, 39:327-328 134-136 Phenylstiboles, 39328, 330 Phenylethynyl ligand, 3889, 116. 121 Pheromones, insect, by metathesis of unsat- Phenylethynyl-manganese complexes, urated esters, 12485 38123,136 PhGeH,, dehydrocoupling for polymeriza- Phenylethynyl-metal complexes, 38122-138 tion, 42384-385 Phenylethynyl-molybdenum complexes, [PhHNNPhNaI2[PhN"PhNa].4DME,syn- 38:122, 135-136 thesis, 43339 Phenylethynyl-nickel complexes, 38128, [(p-PH2)2M2(CO)g]n, structure and bond- 135, 137 ing, 42265 Phenylethynyl-osmium complexes, 38125, PhMeSiH?, dehydrocoupling for polymeriza- 136 tion, 42373, 381, 387, 393 Phenylethynyl-palladium complexes, 38128, PhMezSiH, synthesis, 42393 132, 135, 137-138 Phosphaalkenes, 39214, 218 Phenylethynyl-platinum complexes, 38:128- phosphorus heterocyclic compound syn- 132, 135, 137-138 thesis, five-membered rings, 4k16-20 Phenylethynyl-potassium complexes, 38122 transition-metal complexes, 41:2 Phenylethynyl-rhodium complexes, 38124- Phosphaazasilacyclobut-3-ene, 39219 127, 137 a-Phosphacarbollide (B9H9CHP") com- Phenylethynyl-ruthenium complexes, plexes, 8101-103 38124-125, 136 Phosphacymantrene, 39:333 Phenylethynyl-tin complexes, 38122, Phosphadistannacyclobutene, 39316 135-136 Phosphaferrocenes. 39325 (Phenylethynyl)titanocene, 32263 electrochemistry, 39343-344 Phenylethynyl-tungsten complexes, 38122- molecular structure, 39333 123, 134-136 reactions, 39345-347 Phenylethynyl-vanadium complexes, 38122, [l]Phosphaferrocenophane, 32154 136 Phosphanylorganyldiazenes, 23167-168 Phenylethynyl-zinc complexes, 38122, Phosphasilenes (silylidenephosphanes), 135-136 39194-195,344 Phenyl group, substitution on Si. M80 metastable, 39199-200 1-Phenylheteroles, 39326 synthesis, 39199-204 Phenylisocyanate, reaction with iminosi- molecular and electronic structure, lane, 39174-175 39195-1 97 Phenylisosilacyanide, preparation, 39161 reactions, 39209-220 Phosphasilenes (silylidenephosphanes) 250

with alkynes and cyclopentadiene, Phosphine ligands 39212-213 hydrogen-deuterium exchange, 15149, with benzophenone, 39213-214 154-156 cycloadditions, 39216-219 intramolecular ring closure reactions, with diphenyldiketone. 39214-215 15149-154 protolysis. 39210 Phosphine ligands. effects in catalysis with sulfur, 39211-212 chirality and asymmetric hydrogenation, with tellurium, 39211 12427-428 thermolysis, 39209-210 ethylene-butadiene codimerization with white phosphorus, 39210-211 by cobalt and iron complexes, spectroscopy, 39204-206 12310-313 transient, 39197-199 nickel catalyst activity, 12295-297 X-ray diffraction, 39206-208 stereoselectivity with nickel complexes, 1,2-Phosphasiletane, thermolysis, 39197 12300-302 Phosphastannacyclopropene, 393116 stereoselectivity with rhodium com- Phosphidc derivatives, multiple bonding, plexes, 12285-290 3926-38 hydroformylation, 1220-32 Phosphine boranes, 9300 hydrosilation Phosphine complexes. 85, 8, 14 by platinum complexes, 12413-414 bridged, see Bridged phosphine com- by rhodium complexes, 1E432-433 plexes nickel-catalyzed oligomerization, 12121, carborane, 3331-332 123-124 chromium, 3201-204 Phosphine methylenes, 9290-300 cobalt, 3237-243 coordination compounds, 9299-300 diboranes, 3281-283 proton exchange, 9293 iridium, 3:244-247 synthesis and properties, 9291 iron, 3224-225,229-234 Phosphine monocarbonyl complexes, for- manganese, 3214, 216-219, 221-222 mation mass spectra, 6:294, 302-303 hafnocene, 25371-372 fragmentation patterns, 6296 titanocene, 25351-358 molybdenum, 3201-204 zirconocene, 25365-366 nickel, 3247-250 Phosphines, reactions osmium, 3236-237 formaldehyde, 38165 palladium, 3251 manganesepentacarbonyl alkyl, platinum, 3251 32194-197 rhenium, 3223-224 molybdenum and tungsten alkoxides, rhodium, 3243-244 22351-352 ruthenium, 3236 pentadienyltricarbonylmanganese com- tungsten, 3201-204 plexes, 26150 vanadium, 3195-196 rheniumpentacarbonyl alkyl, 32211-212 Phosphine derivatives, of anionic transition trimethylenemethane metal complexes, metal hydrides 22297-298 reactions, 2232-34 Phosphines, tertiary, see Tertiary phos- with alkyl halides, 2235, 37-41 phines with electrophiles, 2233 Phosphine sulfide, 32161 spectroscopic properties, 225, 21, 23-27 Phosphinic acid, dimerization, U42-43 structural characteristics, 229-10, 12-20 Phosphinimines, %284 Phosphine imides, 9272 alkalimetal derivatives, 9285 alkali metal derivatives, 9276 aluminum alkyls, 9288-289 aluminum compound, 9275 Group IV derivatives, 9308-314 251 Phosphorus ylids

quaternization, 9315 bisphosphines, 19294, 296-301 Phosphinites, 38164 cyclooctenyl nickel derivatives, 19295 (Phosphino)(acyl)carbenes, reactivity, J3,p-13c values, 19296 U188 heterocarborane, 30140-145 (Phosphino)(alkyl)carbenes, reactivity, polarographic reduction, 30:142 44A87-188 reaction, 30.141-144 (Phosphino)(amino)carbenes, reactivity, structure, 30142-143, 145 U200-201 synthesis, 30141 Phosphinocarbenes transition metal complex, 30143-144 2-electron ligands, 44:209-210 ionization potential, 30198 44:210-213 4-electron ligands, multiple bonding, 39193- 194 RZP-C-X nucleophilic displacement reactions, Group 1 element, M187 20308 14 M187-194, Group element, n complexes, 26:282-284 196-200 carbollyl complexes, 26282 Group 15 element, U200-203, cyclopentadienyl complexes, 26282 205-208 structures, 26283 Group 16 element, 44:208 reaction with alkyl halides, 3872 spectroscopic data, 44:183-186 terphenyl derivatives, U41-45 synthesis, 44:179-183 white phosphorus, 39210-211, 223, theoretical studies, U177-179 26 6 - 2 6 8 X-ray analysis, 44A83-186 Phosphorus-bridged [llferrocenophanes, (Phosphino)(nitroso)carbenes, reactivity, M202 ring-opening polymerization, (Phosphino)(phosphonio)carbenes 32153-160 deprotonation, 44:182-183 Phosphorus-gold bond, 38119 reactivity, M205-208 Phosphorus-silicon multiple bonds, solid-state structure, U.185-186 39193-1 95 theoretical studies, M179 phosphasilenes (Phosphino)(phosphoryl)carbenes, reactiv- metastable, 39:199-220 ity, a203 transient, 39197-199 (Phosphino)(silyl)carbenes, reactivity, theory, 39195-197 44:189-194, 196-200 Phosphorus(V) alkyls, 14214-224 (Phosphino)(stannyl)carbenes, instability, Phosphorus ylides M200 bonding, 14212-214 Phosphirene derivatives, 13148 d-orbital participation, 14212 Phosphites, 38:164 dipole moments, 14:212 Phosphonate arene osmium(I1) complexes, effect of silylation on stability, 29200 14228-229 Phosphonio cyclohexadienyl ruthenium NMR data, 14212 complexes, 29214 photoelectron spectra, 14214 Phosphonitrilic systems, 9341 properties, 14210-21 1 Phosphonium ylides, comparison with arse- reactions, 14210 nic, 20116 with silacyclobutanes, 14218-220 Phosphorimide complexes, 10164 with unsalurated germanium com- Phosphorus pounds, 39292 bimetallic and trimetallic complexes, structures, 14211 37:304 synthesis, 14209-210 donor ligand complexes, "C NMR spec- vibrational spectra, 14211 troscopy Phosphorus ylids, 9321-329 Phosphorus ylids 252

bis(phosphoranylidene)methanes, cyclic polymethylsilanes, 19:52-54 9327-328 linear polymethylsilanes, 1954-55 organosilicon derivatives, 9321-325, 339 naphthyldisilanes, 1982-84 coordination compounds, 9:325 phenyl-substituted polysilanes, properties, 9322-324 1958-59 rearrangement reactions. 9324-325 polysilacycloalkanes, 1956-58 synthesis, 9:321-322 Photo Diels Alder reactions, 34103-104 phosphoranylidene methylphosphonium Photoelectrochemistry, of rhenium carbonyl ions, 9~327 complex, 2323-24 Phosphorylidc complexes, from carbene Photoelectron spectra complexes and phosphines, 149-11 arsenic ylides, 14228-229 irradiation, 149-10 arsonium ylides, 20132 Phosphyne, reactions of silenes with, 39:122 bent sandwich complexes, 1534-35 Photocatalysis, of hydrogenation, fluoroolefin complexes, 1526 12378-379 Group 4B metallocene dicarbonyls, Photochemical activation 253.51 catalytic cycle, 32140-141 methyltin halides, 14:67 supported catalysis phosphorus ylides, 14214 Y-A1203,32:143 a-methylenes, 20197, 246 metal phthalocyanines, 32142-143 silenes, 2518 polymeric phosphonium salts, 32142 Photoelectron spectroscopy silica, 32142 sodium montmorillonite, 32143 alkylidynetricobaltnonacarbonyls, 241 18 styrene-divinylbenzene resins, alkynyl-metal complexes, 3883-84 32140- 142 arene complexes, 1351-52 titania, 32142 1,4-diaza-1,3-butadiene ligands, 2k154, triphenylphosphinc ligand exchange, 156 32140- 141 divalent organo-Group IV compounds, Photochemical desulfination, of molybde- 19140-142 num complexes, 12:60 iron borane complexes, 21:73,78, 85-86 Photochemical lability, of aryl-thallium manganesepentacarbonyl alkyls, 32178 bond, 1k171 as probe for aromaticity in heterocycles, Photochemical reactions 13:251-253, 261 acylmetdkids, El26 tetrazene, 24214 bis(germy1) ketone, 2142 MO calculations, 24214 elimination reactions, 2166 zirconocene(q4 -diene) complexes, 2413 photolysis products, 7:128 Photolysis organocobalt compounds, 1k403 acyldisilanes, 2532-35 transition metal carbynes, 27:98 acylsilanes, 3981, 93, 106 Photochemical synthesis, of silenes, 25:9 arydisilanes, 2532 Photochemistry azidosilanes, 39:160 metal carbonyls, 26:297-375 benzodisilacyclobutane, 39111 metal complcxes, 17:320 bisdiazoalkane, 39:109-110 organometallics, 24:249-351 1,4-bis(pentamethyIdisilyl)benzene, organopolysilanes, 1951-95 39~108-109 a-alkenyldisilanes, 19234-88 cyclotrisilane, 39:255 alkynyldisilanes, 19:88-92 diarylbis(trimethy1silyl)germanes. 39287 benzcnoid derivatives of disilanes, 2.2-diazidohexamethyltrisilane, 39183 19:74-82 di-t-butyldiazidosilane, 39:184 branched polymethylsilanes, 1955 di-terr-butyl peroxide, 44.69-70 253 Platinum

1,l-dimethyl-2-phenyl-l-silacyclobut-2- B bonds, of olefin-transition metals, ene, 3984 k195-197 disilagermirane, 44.130 s-Complexes disilylacylsilanes, 3974, 81-82 cyclic hydrocarbons, analysis of spectra, disilylaklenes, 3979 k255-257 disilylalkynes, 3980 of main-group elements, 26217-295 disilylaromatic compounds, 3974, 80 between metals and C, H, ring disilyldiazoalkanes, 3976 C, system, k2.57-258, 260 flash, see Flash photolysis C4 system, k258-259, 262 4-germa-2-pyrazoline, 39294 Cs system, k259-291 hexaarylcyclotrigermanes, 39:287 Ch system, k291-302 hexakis(2,4.6-triisopropylphenyl) C7 system, k303-304 cyclotristannane, 39209 Cx system, 1:306-307 hexamesitylsiladigermirane, 39287 Pinacolic coupling, with magnesiumgraph- iminosilanes, 39160-161 ite, 28126 methylphenyldisilybenzenes, 3999 , reactions with silenes, 39113 l-pentamethyldisilyl-4- Platinum trimethylsilylbenzene, 39109 v3 allyls, 19178 platinacycloalkanes. 27:152 I3C NMR data, 19279-281 polysilylacylsilanes, 3974, 81-82, 93, 143 basic behavior with environmental change, B266 polysilylalkenes, 3979 carbonyl cations, 8158-159 polysilylaromatic compounds, 3974, 80 a-cyclopentadienyl-n ally1 dimetal com- silene formation, 39140 pounds, 19158-160 silyl azide, 39161 high nuclearity carbonyl clusters, 14287 silyldiazoalkanes, 3974-76, 146 reactions, 14335-336 tetrakis(2,6-diethylphenyl)digermene, structures, 14288, 296-298 39303 synthesis, 14334-338 trigermirane, 44:129-130 intermolecular coordination systems trisilanes, 39232-236, 254 platinum(II), X39-49 [{Ph3PAu],N]*+,synthesis, 4290 platinum(IV), M.49-55 [ [ Ph,P] Csz(C5Hs),], synthesis and structure, metallacycles, 2697 43297 metalladisiloxanes, 19244-245 PhPH2, dehydrocoupling for polymeriza- mixed alkali metal compounds, 27:251, tion, 42386-387 256 [(PHPh)Fe2(C0)6]2(P3Ph3)rsynthesis, 4280 mixed-metal clusters, 18210-212, 214, [Ph4P][Na(C5H&], synthesis and structure, 2 16-2 17,220-226 43296 cobalt carbonyls, 18236-237 [(Ph3P)2Pd]2As2,structure and bonding fac- rhodium carbonyl anions, 18:238-239 tors, 4250 nitrogen donor ligands, 342-38 PhSiH,, dehydrocoupling for polymeriza- organometallic chemistry of five-coordi- tion, 42369-370, 376, 380-381, 387 nate(I1) complexes, 3423-26 PhSiH(NMeNHMe)2, synthesis, 42395 platinum(1V) complexes, 3426-38 PhSiH2(NMeNHMe),synthesis, 42395 poly(pyrazo1-1-yl) alkane ligands, 54:2-38 (Ph2SiH)20,synthesis, 42:391 poly(pyrazo1-1-yl) borate ligands, 34:2-38 Phthalocyanines, organocobalt derivatives, radicals, from homolytic substitution reac- 1k364 tions, 14373-383 Ph(W(CO),),Sb(PPh,), synthesis, 42101 in silacyclobutane polymerization cataly- Physiological action, organometallic com- sis, 19215-216 pounds, 7:30 silyls Platinum 254

as hydrosilation catalysts, 19251 carbene. 147 reaction with HCI, 19248 carbonyl, 3251 square planar(I1) complexes, 347-23 catalysis of third-order nonlinear optics of squarc-pla- alkane reactions, 38167-170 nar complexes, 43375, 377-378 hydrogen exchange in benzene, 13275 in triosmium clusters, 26:76-80 catalysts Platinum, binuclear hydride complexes in hydroformylation, 1254-55 dimeric alkynes, 22237 in hydrosilation, 12408-428 efectruchemistry. 22256 chirality and asymmetric synthesis, isocyanides, 22237-239 12427-428, 434 oxidative addition, 22261-263 with chloroplatinic acid, 12408-427 triangular clusters, 22223, 249-250, in catalyzed decomposition of formic 261-262 acid, 22141 Platinum chloride dialkyne, 30215 cyclopropane complex. 326 1,4-diaza-l,3-butadienes ethylene complex, 348 bridged binuclear compounds, 21:158, Platinum chloride-TPPTS complex, 38176- 160-161, 165-166 177, 183 with chelated ligand, 21:159, 162-164, Platinum-chlorine bond, 3&117-119 169, 189-192,203 Platinum clusters, with more than two dif- with monodentate ligand, 2k159, ferent metals, 3k376-383 162-164 bridging alkylidyne. 31:380-383 direct platinum-carbon coupling con- heptametal chain, 31:382 stants, U:159-160, 193 iron and tungsten, 31:380 disilene, 39:268-269 isomerization, 3k381 dynamic, 30181 nickel and tungsten star, 31:381 open chain polymetallic species, electron-transfer reactions 31580-381 mechanisms of aryl oxidation, 2335-36 tri- and tetra-nuclear palladium species phosphines, 2333 bridging allylic ligand, 31:379 ethanol electrochemical study, 3k379 mt rearrangement. 16:250-252 isomerization, 3k379 X-ray studies, 16250-251 preparation, 31:377-379 fullerenes, -71-72 Platinum complexes hexafluorobenzene, 3kl99-200 acetylenes, 13299-301 homoadamantyne, synthesis and struc- alkyl, 38108 ture, 42194-195 alkyliyne carbaborane, 3k60-61, 77-81 iminooxosulfuranes, 36185-186 alkylplatinum( 111), 38162- 163 isocyanide, 11:75-80 alkynyl, 3887-89. 108, 111, 113, 117-118, addition of alcohols and amines, 11:46 139 main group anionic carbonyl clusters, 22199 tellurium, 3k168-169, 173 anionic hydride thallium, 31:108 as catalyst, 2246 via metal atom synthesis, 15100 spectroscopic properties, 275 insertion reactions, 15103 arenes, 13118-120 p-methylenes, 20179-180, 200 bcnzdiyne, synthesis and reactivity, with ditertiaryphosphine bridges, 42177 20179-180 bimetallic, 37:229-230. 237, 240-241, trinuclear clusters, 20185 255-256.258-261 mixed-metal clusters boranes. 21:64-66, 68, 75, 82, 96, 104 cobalt nitrides, 2463, 68, 71 -73 Platinum(lV)

electron-transfer reactions, 24111-1 12. in alkanes, 15165-174 121, 124 effects of ligands, 15167-169 iron nitrosyls, 24:49 mechanism, 15169-172 olefin, I3C NMR data, 19:270-271 nature of catalyst, 15:167-172 perfluorobicyclo[3.3.0]octadienyl, nature of reaction mixture, 15165-167 3k240-241 rate vs. ionization potential of alkane. phenylethynyl, 38128-132, 135, 137-138 15172-173 photochemistry relative reactivity of alkanes, alkylbipyridyl derivatives, 24322 15172-174 alkylbis (phosphine) halides, steric effects, 15173-174 24320-322 in alkenes, 15176 binuclear phosphinemethyls, in alkyl groups, 15174-176 24323-324 of chloroalkanes, 15175 cyclooctadienediisopropyl,24322 in benzene ring, 15158-165 cyclopentadienyltrimethyl, M322-323 exchange rate, 15159, 162 dialkylbis (phosphine) derivatives, multiple exchange, 15161 24f319-320 reaction schemes, 15159-165 metallacyclobutanes, 24316-317 Platinum(I1) complexes, 28220 metallacyclopentanes, 24f31.5-318 direct arylation of, with Grignard and or- reaction with methylcobalamin, ganolithium reagents, 28:221-226 20318-319 perhalophenyl mechanism, 20335, 337 with one CbXsgroup bonded to each redistribution reactions, 2396 metal center, 28:229-240 alkyls, 23119-122 with three C6Xs groups, 28256-266 phosphine halides, 23107, 114, with two C,X, groups bonded to each 116-117 metal center, 28240-255 $-SiH, 30:177-178 Platinum(II1) complexes, 28:277-278 substitution reactions Platinum(1V) complexes, 28279-280 acetylenes, 10352-354 Platinum(IV), organic chemistry, olefins, 10:356 27~113-168 sulfines, 36975 carbenes, 27:159 sulfur diimides, 36:204 carbonyl complexes, 27:158-159 sulfur dioxide insertion reactions, a69 crystallographic data, 27:122-123 with thiazate ligands, 36:219 cycloalkane derivatives, 22148-158 trans-effect, 1517-18 P-diketonates, 27:145-148 trans-influence, 1517-18 diorganoplatinum(1V) compounds, trimetallic, 32246, 265 27:117-126 trimethylenemethane isocyanide derivatives, 2R160-161 role in organic synthesis, 27:305-307 monoorganoplatinum(1V) compounds, structure, 27:294 27:114-117 tropyne, synthesis and reactivity, tetraorganoplatinum(1V) compounds, 42:181-182 22143-145 vinylidenes, 2271, 94 triorganoplatinum(1V) compounds, and carbene formation, 22:94-95 22126-143 ylides, 20153 bond lengths and angles, 27A38 Platinum( I) complexes, binuclear metal chemical properties, 22141-143 containing bridging ligands, 28:280-287 Group V and VI donor ligands, without bridging ligand, 2k287-288 22127-131 Platinum(I1)-catalyzed H-D exchange, halides and pseudohalides, 27:126-127 15158-177 spectroscopic properties, 22131-143 Platinum compounds 256

Platinum compounds rotation and localized exchange in carbene, 11:40 Ptb, and PtL3, group, 3k317-320 carbonylation, 11:138-139 MO calculation, 3k319-320 silyl, 1k259-260 olefinic and phosphine environment in hydrosilylation, 11:302-303 exchange, 3k320 silylmethyl, 1k318 ‘*’OSNMR coupling, 3k317 &Platinum diacetylides, 31257 phosphine substitution effect, Platinum hetcronuclear clusters 3k317-318 bimetallic, 31:301 triangular comparison, 3k319 bonding and electron counting, isomerization, metal core rearrangement, 3k306-312 3k327-328 anionic raft, 3k310 effect of ligand, 31:328 dianion hypothetical, 31511 isotopic labeling, 3k328 frontier orbital, 31:306-307 kinetic study, 3k328 high nuclearity, 31:309 site-specific reactivity, 31:302 molecular orbital study, 3k310-312 structural and reactivity aspects, nonplanar, 3k309 31~328-383 nonutilization of tangential orbital, palladium platinum, 3k376 31~306-307 synthesis skeletal electron pair theory, carbonylate anion with halide complex high nuclearity, 3k30.5 3k306-308 metal exchange, 31:305 tetrahcdral, 3k309 redox condensation, 31:30.5 topological electron counting theory, carbonylation of metal halide, 3k305 31:306-307 saturated carbonyl complex triangular, 31:308 cobalt triad, 31:303-304 trigonal bipyraniidal, 3k312 iron triad, 3k303 utilization of tangential orbital, 3k310 phosphine, 31:304 valence electron, 3k307-308, 312 unsaturated carbonyl complex fluxional behavior, 3k312-327 isolobal analogy, 3k304 exchange spectroscopy, 31:315-317 osmium, 31:304 intermetallic ligand migration, 31:315, rhodium, 3k304-305 32 2 - 3 2 6 Platinum metals, carhonyl halides, 814-15 carbonyl exchange, 31:322-323 carbonyls, 8:16-17 carbonyl migration in anionic com- complexes, mass spectra, 8280, 283 plex, 3k322-323 Platinum-platinum bond complexes, 331-2 frce energy of activation, 31:325 Platinum, zero-valent complexes, addition hydride exchange, 3k323-326 to localized exchange in ML group metal carbenes and carbynes, 18231-233 iron and cobalt triad, 3k320 osmium carbonylhydride, 18:232 rocking motions, 3k321 unsaturated metal-metal bonds, tripodal rotation, 31:320-322 18:231-233 metal framework rearrangement, Plumbocene, see Dicyclopentadienyllead 3k315, 326-328 Plumbosiloxanes, 1298 butterfly core geometry, 3k327 [P,(M(C0),)l3~,synthesis, 42:88 carbonyl scrambling, 3k327 (PMDTA)K(~-CHR,)K(~-CHR~)ZK((/.L- time-averaged mirror plane, 31:326 CHR,)K-(PMDTA), synthesis and metal-localized ligand scrambling. structure, 43:283 31:315 Pnictogen bonding, 39339-340 “‘Pt NMR, 31:312-315 Pnigogens, symbol, 2160 257 Polyhedranes

Pockels effect, 42296,298 properties, 32156 Polarization measurements, 2138, 140 Poly(ferroceny1phosphine oxides), 32153 Polarization transfer NMR spectroscopy, Poly(ferrocenylsilanes), 32136, 139-141, 23193-218 164 Polar ligands, oxidative addition of, com- ceramic precursors, 37:150-151 puter representation, 26176 properties, 32141-150 Polarographic reduction, 2119-120 Polyfluoroalkyl, derivatives Polonium compounds, by @-decay of organ- lithium, k145 obismuths, 1k235-236 magnesium, 1:145 Pol y acenes, 2 138- 139 manganese, 1:186, 191,206 Polyalkenamers, via olefin metathesis, mercury, k202 16284. 305-306 silicon, k161-163 cycloheptene, 16305 tin, k166-170 cyclooctene, 16305 transition metals, k181-182, 186-195, cyclopentene, 16284 214 1-methylcyclobutene, 16305 Polyfluorocarbon-metal derivatives, NMR norbornene, 16:284 of As, B, Ge, Hg, Si, Transition metal use of tungsten carbene complex, Zn, k212 16305-306 Polygermanes, 442-43 Polybutadiene, industrial use, 12142 antiiadder, 3212, 14 Polycarbosilanes, 32150 cage, 3212-14 Polycondensation reactions, 37:132 cleavage of Ge-Ge bond, 445-47 Polycyclic boranes, 2277 ladder, 3212-14, 19 Polycyclic ketones, conjugate addition of preparation, 438-41 Grignard, k223-228 from germanes, 441 Polycyclic polystannanes from halogermanes, 4:38-41 properties and reactivity, 38237-239 properties, 444 structure, 38234-237 reactions, 445-47 synthesis, 38232-234 spectra, 444-45 Polyethers, complexes with organomagnes- synthesis by dehydrocoupling, 42384-385 ium compounds Polyhalo compounds, reactions with organo- cleavage reactons, 32:176 lithium compounds, 7:46 coordination geometry, 32176-177, 182 Polyhalogenoalkanoates, metal, thermal de- crown ether reactivity, 32:175-184 carboxylation, 23243-246 dialkylmagnesium reagents, 32175-176, Polyhalogenoarenecarboxylates,metal, ther- 178 mal, decarboxylation, 29248-254 diarylmagnesium reagents, 32180 main group element compounds, dissociation, 32178 29252-254 threaded complexes, 32178-179 transition metal derivatives, 29248-252 Polyethylene, from ethylene via nickel cata- Polyhapto-coordinated mixed metal com- lyst, 12122 plexes, 22208-212 Polyferrocenes, 8:258 Polyhedral skeletal electron pair, 263-4 Poly(ferroceny1ene persulfides), 32133, 157, Polyhedranes, 321-2 160-162,165 hexasilaprismane, 321-4, 23-26, 36 Poly(ferrocenylenes), 37:135, 149 octagermanes, 3217-14 Poly(ferrocenylethylenes), 32156 octasilicubane, 321-4, 14-17, 36 Poly(ferrocenylgermane), 32152 octastannacubane, 3219-22 Poly(ferrocenylmethylene), 32156-157 precursors, 326 Poly(ferrocenylphosphine), 3R154-155 reducing reagents, 326-8 from condensation reactions, 32153-154 substituent selection, 375 Polyhedranes 258

tetrasilatetrahedranc, 321-4, 8, 34-36 with trithio- or dithiocarbonate bridges, Polyhydric alcohols 28249-250 from CO and hydrogen, 1280-83 Polynuclear transition metal complexes, mo- from COz and hydrogen, 1281 lecular rearrangements, 16319-346 Polyhydridofarenefruthenium,preparation dinuclear carbonyls, 16:323-326 from ruthenium(I1) complexes, 29179 heptanuclear, 16330 Polyimino complexes, 22274-275 hexanuclear, 16330 Polyisoprene, industrial use, 12142 hydride carbonyls, 16332-336 Polymer-bound cyclopentadienyl com- isocyanides, 16332 plexes, 2k46-51 NMR spectral data, 16320-323 Polymerization I3C NMR studies, 16319-320 alkali metal organics, 27:179-180 olefin complexes, 16336-341 anionic, masked disilenes, 3838-39 dinuclear, 16336-338 atom abstraction-induced, [3]trithiaferro- skeletal atom migration, 16341-343 cenophanes, 32160-162, 164 tetranuclear carbonyls, 16:328-330 diazoalkanes, %424 trinuclear carbonyls, 16326-328 dienes, inhibition by acetylene cobalt car- Polyoxometallates, organometallic, honyl complexes, 6165 28382-387 dienes and olefins Polyphenyl alkali metal compounds, radical via organolithium catalysts, 1855-97 anions and dianions, 22205-206 via Ziegler-Natta catalysts, 1894-149 Polyphosphanes, synthesis by dehydrocou- olefins. by titanium-aluminum com- pling, 42386-387 Polyphosphazenes, 37:133 pounds, 9182-185 Polyplumbanes, 468 a-oletins, by silylmethyl complexes, cleavage of Pb-Pb bond, &73-77 11:322 dissociation, 472-73 by organolithium compounds, 4272-278 preparation, 465-69 organopolysilanes. 679 reactions, 473-77 by organozinc compounds, U:116-119 spectra, 471 ring-opening, see Ring-opening polymer- thermal stability, 469-70 ization Poly(pyrazo1-1-yl) alkanes transition metal carbynes, 2294 ( ~3-allyl)palladium(11) complexes, 342-7 Ziegler-Natta, see Ziegler-Natta polymer- bidentate ligands, 346 ization binuclear complex, N4,6 Ziegler-Natta catalysts, 6:12 bridge inversion, 346 Polymerization reactions, catalyzed by al- double salts, 34:7 kali metal GIC, 28110-111 fluxional processes, 345, 7 Polymers NMR spectra, 345-7 ferrocene-based, 32134- 136 reactions, 342-5 of organoplatinum compounds, five-coordinate platinum(I1) complexes, 22117-118 3423-26 transition metal-based, by ring-opening NMR studies, M23-24 polymerization, 32131 -165 structures, 3425 Polymethyl-1.1 '-diheteroferrocenes, spec- intramolecular coordination systems, troscopy, 39342-343 3439-55 Polynuclear carbonyl anions, 84, 6, 11-12 palladium(1V) complexes, N34-38 Polynuclear carbonyl hydrides, 88 geometry, 3437 Polynuclear perhalophenyl complexes of iodoethane addition, 3438 Pt(I1) and Pd(1l) NMR spectra, 3437-38 halide-bridged, 28250-252 reductive elimination, M38 259 Polysilanes

structures, 3436 1Polysilanes, 413-23, 32150, 38190, 210, synthesis, M34-35 212, 3974, 80, 128 platinum(1V) complexes, 3426-38 alkenyl and alkynyl, 677-80 cyclomet allation, 3435 properties, 678 dimethly complexes, 3426-27 synthesis, 677 geometries, 3433-34 applications, 42:367 iodo complexes, 3432-33 with carbon-functional groups, 6:65-77 NMR spectra, 3429-30, 34-35 reactions, 6:71-77 reactions, 3426-27, 29-30, 32-34 synthesis, 665-70 structures, 3428, 31 chemical properties, 430-38 trimethyl complexes, 3427, 29 chloromethyl derivatives, 6:65 square planar dimethylgold(II1) com- reactions, 666, 71-74 plexes, 3411 cleavage of Si-Si bond, 431-35 square planar palladium(I1) complexes, cyclic, 3k37 M7-20 decaphenylcyclopentasilane, k125-130 chloro-bridged complexes, 348 dodecaphenylcyclohexasilane, cyclometallation, 348 k130-132 dimethyl complexes, 3419-20 octaphenylcyclotetrasilane, k117-125 fluxional complex processes, 349-11 structural studies, 1:94-102 fluxional motion, M11-12 ladder polysilane, 37:lf intramolecular coordination, 349-10 linear iodo complexes, synthesis of, 3417-19 nomenclature, k93 NMR spectra, 345-10, 19, 22-23 preparation, k105 properties, 1:133-136 Pd(Ci3HiJ'J) {(pz),BH), 349 peralkylated, 6:46-65 ~P~(C,H~)),((~~)-IB-B(~Z),J,34:s chemical properties, 655-65 phosphines, 3412 halogen cleavage, 655-58 reactions, 347-8 oxidation, 659-61 square planar platinum(I1) complexes, reaction with alkali metals, 662-65 3413-23 with peroxides, 655 chloro-bridged complexes, 348 synthesis, 652-54 cyclometallation, 348 thermolysis, 654 dimethyl complexes, 3420-21 permethylated PtMe((pz),BH)(CO), 3414 properties, 649-51 synthesis of, 3414-16 synthesis by alkali-metal coupling, Poly(pyrazo1-1-yl) borates 646-48 (~3-allyl)palladium(II)complexes, M2-7 by methylation reaction reactions, five-coordinate platinum(I1) complexes, 648 3423-26 UV spectra, 6:84 methylpalladium(I1) complexes, 3456-62 permethylated polycyclic, 3833 palladium(1V) complexes, 3434-38 photolysis, 2933-35 platinum(1V) complexes, 3426-38 preparation, 43-12 square planar palladium(I1) complexes, coupling reactions, 44-6 347-20 from cyclosilanes, 47-11 square planar platinum(I1) complexes, from hexahalodisilanes, 4:4 3413-23 use of silyl-metallic reagents, 46-7 trimethylpalladium(1V) complexes, properties, 636-37 34:56-62 from halogen compounds, 634-35 Poly(ruthenocenylethylenes), 32160 by hydrohalogenation of cyclosilanes, Polysilacycloalkanes, photolysis. 1956-58 636 Polysilanes 260

synthesis, 634-36 NMR, 38202-203,212-214,216-217, radical anions, l5305-306 227-228, 238 reactions, 431-38 vibrational, 38199-202 spectra, 4:24-29 synthesis by dehydrocoupling, 42385-386 infrared and Raman, 424-26 thermal stability, 453 NMR studies, 428-29 Polystyrene, as support for transition metal ultraviolet, 4:26-28 catalysts, 15197-201 synthesis, 3834-37 Polystyrene-linked triosmium clusters, as synthesis by dehydrocoupling catalysts, 2663-64 backbone functionalized poly(pheny1si- Polytin dihydrides, 1:50 lanes), 42382-383 Poly(vinylferrocene), 32134, 146 catalysts, 42368-373 Poly(vinylsilane), synthesis by dehydrocou- complex hydrosilanes, 42382 pling, 42383 limitations, 42367 Porphyrins mechanistic considerations, 42373-379 organocobalt derivatives, 1k364 preceramic polymer applications, tin, 982 42383-384 Potassium stereoselective dehydropolymerization, bis(tetrahydr0furan) compounds, 42379-381 26224-225 thermal stability, 424 catalyzed reactions Polysilanyl anions, 3825-39, 52 of alkylbenzenes with ethylene, 16182 Polysilanyllithiums, 3826 of 1-methylnaphthalene, 16183 Polysilapolyhedranes, 328 cyclooctatetraene salt, 26224-225 Polysiloxanes, 37:133 fluorenyl complexes, 26:224-225 Polysilylacetylenes, 3988 metal-carbon bond lengths, 43342-343 Polysilylacylsilanes, 3974, 81-83, 93, 143 phenylethynyl complexes, M122 Polysilylalkenes, photolysis, 3979 physical properties, 27:174 Polysilylalkynes, pyrolysis, 3974, 80 reaction with acyclic pentadienyl ligands, Polysilylaromatic compounds, photolysis, 26127 3974. 80 safety in handling organometallic com- Polysilylcarbinols, silene synthesis from, pounds, 43269 39:74, 79 salts, of anionic transition metal hydrides Polysilyldiazoketone, 39147 spectroscopic properties, 225-8, 21 Polysilyllithium reagents, silene synthesis structural properties, 27:12-14, 18-19, from, 3978 24-25 Polystannanes, 454-57, 38189-190 solvation energy, 22182 branched polystannanes, 38215-217 structure determination of organometallic cleavage of Sn-Sn bond, 4:59-63 compounds, 43268, 271-272, 342 cyclopolystannanes, 38217-232 zeolites, 22237-238 distannanes, 38190-204 Potassium, acyclic pentadienyl complexes linear polystannanes, 38:205-215 conformers, 26128 polycyclic polystannanes, 38232-239 reactions with preparation, 448-53 electrophiles, 26132 from tin halides, 448-51 metal chlorides, 26:135-138, 141 from tin hydrides, 451-53 metal halides, 26:130 properties, 453, 58-59 transition metal chlorides, 26141 reactions, 459-63 structure, 26128 spectra, 43-59 Potassium, organometallic compounds, X- spectroscopy ray structural analysis, 22169-277 electronic, 38199-202, 210-212 aggregation, 22179-181 261 Propenal

alkyls, 22191-192 P,(PtPR&, synthesis, 4293 alkynyls, 22194-196 Praseodymium, mixed alkali metal com- benzyl compounds, 27:198-200 pounds, 22251 biphenyl radical anion, 22206 Prethermal reactions, in radiochemistry, bond lengths, 22186, 188-189 1k242-244 bridging, 2R177-178 Prismanes, 321,4 without carbon-metal interactions, electronic absorption spectra, 3231 2%239-243,245, 248-259 hexagermaprismane, 321-2, 26-29, 31, charges delocalization, 27:173 36 coordination, 27:176 hexasilaprismane, 321-4,23-26,36 cyclooctatetraene compounds, 22204-205 photochemical reactions, 37:31-34 cyclopentadienyl derivatives, 22203 structures, 3229-31 graphite intercalates, 27:206-207 1,2-Propadiene. reactions ionicity, 22176 with decacarbonyldimanganese, mixed metal compounds, 22208-211, 26358-365 213,216,218-235 with 1,3-ditungstacyclobutadienes, Potassium, synthesis and structures of or- 26111-115 ganometallic compounds Propadienylidene complexes alkene derivatives, overview, 43:309, 311, clusters, 22121-122 326 IR spectra, 2299, 110-112 alkylalkoxide intermediates, 43:291-292 physical properties, 2299 alkyl group exchange, 43:270 binuclear, 22111 alkyne derivatives, 43326 mononuclear, 22110 ally1 derivatives, 43311-313, 315-319 preparation, 2282-86 arene derivatives, 43326-332, 334-341 reactions, 2286-87 azaallyl derivatives, 43:319-320, 323-324 structural parameters, 22:99, 103 azulene derivatives, 43307 Propargyl alcohol, 3248-49, 52 benzyl and related derivatives, Propargyl complexes 43271-275 bimetallic complexes, 32242 cumyl derivatives, 43275, 277 binuclear, structure, 3287-90 cyclopentadienyl derivatives mononuclear, 3293-97 substituted derivatives, 43299-301, 304 structure, 3283-87 unsubstituted derivatives, 43:294-297, reactivity, 32107-124 299 as source of allenyl groups, 3253-64 fluorenyl derivatives, 43305-306 allenyl transfer reagents, 3262 fullerides, 43:341-342 binuclear allenylidenes, 37:62-64 indenyl derivatives, 43304 metal fragment condensation reactions, methyl derivatives, 43271 3257 organolithium reagents, a269 with metal propargyls, 3257-62 organomercury reagents, 43269-270 from propargyl ligands, 3753-56 pentalene derivatives, 43:308 synthesis, 37:42-52 phenyl derivatives, 43292-294 transition metal propargyl complexes, silicon-substituted alkyl derivatives, 37:45-48 43280,283-286,288-289,291 Propargyl halides, 3253 triphenylmethyl derivatives, 43277, 280 Propargylic organozinc compounds, addi- Potassium tris(3,5-dimethylpyrazolyl)borate, tion reactions, l2109 29167 Propargyl-iron complex, in vinylketene syn- Potentiometric titration, 2120 thesis, a332 P3{P(SiMe3),){PP(SiMe3)Z),structure and [1.1.1] Propellanes, 3tk235, 238 bonding factors, 4270 Propenal, reaction with silenes, 39125 Propene 262

Propene Pseudohalide derivatives, of mixed alkali hydroformylation, 28200, 38175-176 metal compounds, 22231-232 metathesis to ethylene and butene, Pseudohalides, organometailic, 5169-224 16284 adducts with Lewis acids and bases, nickel-catalyzed reactions 5196-197 dimerization, 12128-134 bonding, 5189-193 control of regioselectivity, 1’1:128 chemical properties, 5193-200 influence of phosphines, 12129-131 displacement reactions, 5194-195 influence of temperature, 12134-135 exchange reactions, 5193-194 isomerization, 12123-124 IR spectra, 5177-179 oligomerization, 12116-117 polymers, 5198-199 reaction with properties germenes, M126-127 azides, 5215-217 silene, 39114 fulminates, 5218 Propionaldehyde. catalytic hydrogenation, (iso)cyanates, 5208-210 38:178 (iso)cyanides, 5201 -207 Propion yl nianganesepentacarbonyl (iso)selenocyanates, 5218-219 instability, 3T192 (iso), 5211-214 synthesis, 32172-174 reactions of pseudohalide group, Propionyl rheniumpentacarbonyl, synthesis, 5199-200 32176 solvolysis, 5193 Propylene structural isomerism, 5181-189 dimerization with potassiumgraphite com- resonance, 5190 pounds, 28109 synthesis, 5171- 174 hydridonickel-promoted dimerization, by metathesis, 5171-172 12205 from pseudohalogen derivatives, effect of phosphines, 17:205 5172-1 73 palladium-catalyzed eooligomerization by pyrolysis, 5174 with butadiene, 12180 thermal stability, 5175-177 5-Propyl-1-germa-2-oxacyclopentane, syn- trends in properties, 5175 thesis, 43201 ultraviolet spectra, 5179-181 n-Propyl manganesepentacarbonyl, 32170 Pseudohalogens, addition to transition synthesis, 32172-173 metal halides, 279-81 2-Propyn-1-01s. 3249 [Pt(PPh,),{ $-S=C(CF,),]], synthesis, 43:147 Protic acids, reactions of 0s and Ru car- [PtRhIO(C0)21N]”, structure and bonding byne complexes with, 25190 factors, 4238 Protolysis, phosphasilenes, 39210 Pulse radiolysis, metal alkyls, 38158, 162 Proton abstraction reactions, computer rep- Pump-probe technique, third-order nonlin- resentation, 26180, 191-192 ear optics analysis, 43365-366 Protonation Pyranoid glycals, synthesis, 28:117-118 ketene complexes with carboxylic acid, Pyrazolones, conversion into a&-acetylenic 2852-54 esters, 1k200 neutral ketenylidene clusters, 2874 Pyrazolylborate complexes, 10128 Protonic reagents, reaction with germenes. activation of C--H bonds, 15:157-158 a125 Pyrazolyl borate ligand, 3960 [ (i-Pr2PCH2CH2Pi-Pr2)RHJ,(y-H)(p-T2- Pyridine, reaction with disilenes, HSiR?), fluxional behavior, 42277 39257-258 Pseudo-borole, 39380-381 Pyrolysis Pseudo contact shift, in ”C NMR spectra, 1,4-bis(1-methyl-1 -silacyclobutyl) fils1 benzene, 3%75 263 Radiochemistry of organometallic compounds

bis-silene synthesis, 3975 Radical intermediates, in Grignard forma diallyldimethylsilane, 3990 tion, 16144, 193 1,3-disilacyclobutanes, 39:90-92 Radical reactions germanium and bismuth alkyls, of cobalt(I1) complexes, 1k389 2105-106 rate determination by ESR studies, iron silicon carbide ceramics by, 14:347 32150-151 Radicals, see also Nineteen-electron organo- 1-methyl-1-silacyclobutane,3992 metallic radicals; Seventeen-electron or- organoplatinum(1V) complexes, 22126, ganometallic radicals 152 acyl, M96-97 platinacycloalkanes, 22152-154 a-alkoxy, M95-96 polysilylalkynes, 3974, 80 alkoxyl, 44:101 alkyl, M81, 90-91, 94-99 o-(allyloxy)phenyl, a77 Q benzoyloxyl, M99, 101 benzyl, M94 QALE approach, 36:142-143 tert-butoxyl, 44:83, 85, 88, 90, 99 Quadricyclane, reaction with silenes, 39120 tert-butyl, M97-98 Quadrupole splitting, 938-40 Sd-orbital occupation, 970 carbon-centered, M74, 77, 79-81, 86, 88, relation to isomer shift, 9:74-76 90-91, 94-99 clock studies, M73 tin(I1) compounds, 974 tin(1V) compounds, 975 competition kinetic method, M72-73 resolved in tin compounds, 965-68 a-cyano, 44:96 Quinones cyclopropyl, M94-95 reaction with digermenes, a137 cyciotrigermenyl, M132-133 as synthons, 26134 2,2-dimethylethenyl, M94 Quinuclidine wester, 496 fluorenyllithium adduct, 26219-220 kinetic ESR, 44:71 tris( trimethylsily1)cyclopentadienyllithium LFP, M71-72 adduct, 26221 LFP-clock method, a73 LFP-probe method, a72 in metal complexes, computer represen- R tation formation, 26196 Racemization, of chiral metal complexes, reaction, 26:196-197 18172-177 methyl, M86, 88 Radiation damage, in organotin com- neophyl, M74 pounds, 984 nitrogen-centered, M81, 102 Radical anions, 2117-119 a-oxy, 44:98 CICCO~(CO)Q,14103 oxygen-centered, M83, 85, 88, 90, 99, 101 from cyclopolysilanes, 665 rate constants, M70-71 disproportionation, 2124-127 steady-state ESR, 44.71 doublet ground state, 2140, 142 vinyl, M94 electronic absorption spectra, 2132-140, Radiochemical synthesis, organotransura- 145-152 nium element compounds, 9389 hyperfine structure, 2:140 Radiochemistry of organometallic com- organometallic compounds, 15273-313 pounds, 1k207-249 Radical clock method germanium tetraethyl, 1k218, 222 carbon-centered radical, 44.86 metal-carbon CT bonds, 1k221-223 Sn hydrides with acyl radical, M96-97 organoarsenic compounds, 11:221-222 Radiochemistry of organornetallic compoulnds 264

organomercury compounds, 1k222 1,4 addition to a,S-unsaturated ketones, Radioisotope enrichment, 1k216 l2:291-292 Raman effect, k242 alkyne trimerization by cobalt carbonyls, Raman spectra, 3090-92 12369 1,4-diaza-1,3-butadiene complexes, carbon-carbon bond formation via organ- 2k172-174 ocopper compounds. l2259-262 dibismuthine, 3091 cdrbonyl insertion, 11:94-104 digermanes, 444 effect of solvent, 1k97 distibine, 30:90-91 nature of intermediate, 1k97-99 hexaethyldilead, 471 CO exchange in metal carbonyl deriva- hexamethylditin, 458 tives, 3192-193 methyl-arsenic compounds, 4220 copper-catalyzed reactions, 12283-286 polysilanes, 424 desulfination, a50-52 Raman spectroscopy formation of carbyne complexes of 0s and Ru, p-alkynehexacarbonyldicobalt com- 25188- 189 plexes, 12332-334 disilencs, stable, 39:243 cyclopropanes from zinc carbenoids germanium double bonded compounds, and olefins, a87 39285 iridium nitrogen complex, 7:84 n-complexes methylcopper, a221 instrumentation, k251-252 hydrosilylation, 1k300 liquid phase, 1:253 isocyanide insertion reactions, l2:72 solid state, k253-254 organocobalt carbonyls, 3242 vapor phase, k252-253 in organocobalt cluster chemistry, 14140 Raman studies organolithium compounds, 3387-393 on high nuclearity metal carbonyl clus- effect of bases, 3:392-393 ters, 14:310-311 organometallic, 4:268-340 on methyltin halides, 1444-65 organoboron compounds, 4309-324 silicon-transition metal bonds, 11:285 organolithium compounds, 4269-280 Rare earths, see Lanthanides; Organolan- organomagnesium compounds, thanides 4280-289 Rate constants organomercury compounds, 4:289-309 rerf-butoxyl radical, 44.83 organosilicon compounds, 4324-339 Group 14 hydndes, 470-71 organotin compounds, 4324-339 Rates of sulfur dioxide insertion reactions, reductions by effects of organolead hydrides, %279 alkyl and aryl groups, l239-43 pentacyanocobaltate, 1k435-437 ancillary ligands, 1243-44 free radicals, 11:436 solvents, 1244-45 intermediate organocobalt com- Kaylcigh scattering, k242, see also Hyper- pounds, 1k435 Rayleigh scattering substitution, in Group VT metal carbon- KbCSH5,structure, 43294-295 YIS,3196, 207-208 RbCI3H9.PMDTA, structure, 43305 in manganese carbonyl derivatives, [RbCH(SiMe&.PMDTAI2, synthesis and 3219-220 structure, 43283 substitution reactions of metal nitrosyl RbCszCh", superconductivity, 43342 carbonyl complexes, R235 RbCsC,,, superconductivity, 43342 sulfur dioxide insertion, 1248-50 RbC(SiMel)l, synthesis and structure, into iron complexes, 12:38-39 43283-285 into platinum complexes, 1239 Reaction mechanisms reaction intermediates, l238 265 Rearrangements

into rhenium complexes, U39 carbene ligand rearrangement, 25155 into rhodium and indium complexes, ligand substitution reactions, 25154 U39 nucleophilic substitution reactions at into titanium complexes, 12.39 Ca, 25149-153 trans effect, U25 oxidative addition reactions, Ullmann biaryl synthesis, a301 25154-155 Reactions nonheteroatom-substituted carbene (alkyl- separation-induced, 1k241 idene) complexes of zinc carbenoids, l2:84-103 electrophilic addition reactions, Reactions of u-alkyl(ary1) transition metal 25164-166 compounds chalcofonnaldehyde complexes, carbonylation, 7:189 25166-167 cleavage reactions, 2178-189 gold adducts, 25166 of alkyl groups, 2188 reactions with halogens, 25167 alkyl halides, 2183-184 sulfene complexes, 25166 halogens, 7:183-184 nucleophilic addition reactions, hydrogen, 2182-185 25167-168 olefins, 2186 halomethyl ligands as methylene pre- oxygen, 2185 cursors, 25167 protonic reagents, 2178-182 to OS(=CH,)Cl(NO)(PPh,),, reducing agents, 2182-183 25167-168 conversion to n-complexes, 2195 Rearrangement reactions homolytic cleavage, 2187 germanium compounds, doubly bonded, insertion reactions, 2189-195 39303-304 sulfur dioxide, 2191 organosilyl phosphorus ylids, 9324 Reactions, computer representation silene, 39138-149 allyl-alkyl cross couplings, 26202-209 anthracene-silene adducts, 39148-149 anions, 26180 C-H or X-Y additions to C-Si double classification by mechanism, 26174-195 bond, 39140-142 coordination chemistry, -175-191 1,2 shifts, 3k143-145 ethylene dimerization, 26195, 198-199 1,3 shifts, 39:145-148 ethylene hydroformylation, 26:199-202 silylene-silene, 39138-139 format, 26172-174 tin doubly bonded compounds, 39319 intermolecular reactions, 26191-195 Rearrangements Reactivity ally1 groups, 26130, 181, 197 @carbon in organocobalt compounds, anionic germanium derivatives, 161-31 1k397-399 anionic silicon derivatives, 161-31 Ge-N bond, 3:408-412 aryl migrations in organo-Group I com- silenes, 2521 pounds, 16167-210 Reactivity patterns of Ir, Os, and Ru carbenes, 26:181 carbene complexes, 25125-129 cyclopropylmethyl radicals, B.197 effect of metal basicity, 25127-129 dicarbollylaluminum complexes, 26244 with electrophiles, 25127 dyotropic and related u-(Texchanges, with nucleophiles, 25126-127 1633-65 carbyne complexes, 25131-134 fluxional and nonrigid transition metal effect of metal basicity, 25134 n-complexes, 16211-239 electrophilic addition, 25133 Group 111 compounds, 16111-130 nucleophilic addition, 25131 olefin metathesis, 16283-317 N-, 0-,S-, and Se-substituted carbene organoaluminum compounds, 16111-130 complexes organoboranes, 26237 Rearrangements 266

0-sulfinates to S-sulfinates, U:38 mechanisms, 16250-252 pentadienyl anions, 26130 in olefin isomerization, 16260-263 photochemical in olefin metathesis, 16269-271 dimeric aluminum alkyls, 16:103-106 in olefin oxidation, 16252-256 germenes, el23 in olefin polymerization, 16256-260 organoboron compounds, 1684-88 via protonation, 16247 8-U-,10372 via reaction on ligand, 16247-248 nickelocene, 10401 via reaction on metal, 16244-247 in polynuclear transition metal com- in vitamin B12coenzyme-catalyzed reac- plexes, 16319-346 tions, 16275-278 product from sulfur dioxide insertion in1.o [Re2(CO),,($-S=C(C,H,R-p),)], synthesis, metal allyls, 1252-56 43142 tungsten alkoxides, 22320 Recoil energy, y emission, 1k210 unsaturated organoaluminum com- Recoil-free fraction, 9:76-78 pounds, 1667-109 Re6(C0),*(PMe),, structure and bonding unsaturated organoboron compounds, factors, 4231 1667-109 Redistribution equilibria of organometallic Rearrangements, organosilanes, complex compounds, 6171-262 catalyzed, 19213-255 equilibrium constants, 6174-180 disilanes, 19226-233 experimental methods, 6185-193 alkenyls, 19230-232 of families of compounds, 6182 cyclic compounds, 19229-230 NMR techniques, 6186-193 hydridodisilanes, 19:226-229 interpretation, 6187 in reaction with organic halides, theory, 6:173-185 19232-233 thermodynamics, 6:177 mechanism, 19247-251 Redistribution reactions monosilane exchange reactions, aluminum alkyls, 6214 19215-226 beryllium alkyls, 6:203 carbon-carbon, 19215-217 borazines, 6:213 carbon-chlorine, 19223-225 boron compounds, 6206 carbon-hydrogen, 19217-223 cyclic silicon compounds, 6:226 carbon-oxygen, 19225-226 germanium alkyls, 6236, 239-240 hydrogen-chlorine, 19223-225 Grignard reagents, 6205 polysilancs, 19:233 Group I1 alkyls, 6:256 via reductive elimination, 19247-251 Group I11 alkyls, 6218 siloxane, 19234-247 Group IV compounds, 6243,247, Rearrangements, r-n in organotransition 25 0 - 2 5 2 metal complexes, 16241-282 Group V compounds, 6253-254 dinitrogen complexes, 16271-274 Group VI compounds, 6255 dioxygen complexcs, 16274-275 heteropolysilanes, 629 end-on vs. side-on coordination, kinetics, 6:193-196 16271-275 mathematical treatment, 6196-198 factors influencing u-and n-bonding, rapid reactions, 6:199 16242-244 slow reactions, 6194 via hydride abstraction, 16247 lithium alkyls, 6202 in hydroformylation, 16266-268 mechanisms. 6193 in hydrogenation, 16263-266 metal alkyls and metal halides, 2107 importance in homogeneous catalysis, in organodiboron chemistry, 10:258 16241 organolead compounds, 2247 initiation, 16:244-250 silicon-containing systems, 6219-233 Rhenium

cyclic Ge-Si systems, 6228, 230 Reductive elimination cyclic Si-Si systems, 6:228-229 computer representation, 26.173-174, with dimethysilicon groups, 6225 177, 183-184 with methylsilicon groups, 6224 feasibility matrix, 213183 silicones, 6233 geometries, 26.184 system MeSiBr3/MeGeC13,6231 of nucleophilecarbonyl adducts, system MeSiCI3NeGeBr3, 6231 28: 178- 179 transition metal derivatives, 6:256 in organoplatinum(1V) complexes, Redistribution reactions, organotransition 22125-126, 141-142 metal complexes, 2395-129 Reductive elimination reactions, involving alkyls, 23118-126 radicals, 14:388 q3-allyls,23:103-105 Reductive polymerization, CO, 1262 $-benzene, 23126 Reformatsky reactions, lk103-104 carbenes, 23126 with magnesium-graphite, 28:125-126 carbonyls, 23109-111 with titanium-graphite, 28128 in catalysis, 2396-97 with zinc-graphite, 28:114-115 classification, 23:96 with zinc/silver-graphite,28116-117 cyclopentadienyls, 23105-106 Reihlen's structure, 1:3 halides, 23107-109 Relaxation measurements hydrides, 23:116-118 NMR spectroscopy, B450-451 nitrosyls, 23126 I3C NMR spectroscopy, 12:150-151 phosphines, 23112-116 RELAY two-dimensional pulse sequences, spectroscopic studies, 23100-103 28.441 tetraphenylcyclobutadiene, 23111 -1 12 [Re(NO)(PPh)3(O=C(Aryl)H](2- thermodynamics, 23:97-99 C5HSBF4,#/q2isomerization, 0.133 Redox condensation, in synthesis of clus- Reppe reaction, 27:44 ters, 18:233-236, 241 Reppe's complex, k37, 41-42 Redox congeners, 38115-116 Reppe synthesis, 3599 Redox reactions, or trimethylenemethane Repulsion energy, 2123-124 metal complexes, 22298 Residue compounds, 2&89-90 Reducing agents, complex hydrides, 1k11 Reverse saturable absorption, optical lim- Reduction iting analysis, 43356-357, 398-399 acetophenone, 28102-103 [Rh(CO)(v'-S-CH2]($-C5MeS)], synthesis, acyl complex to ethyl, 1269 43153-154 coordinated CO, 1268-73 Rhh(CO),, (p-AstBuz)(p4-AsfBu),structure electrocatalytic, carbon dioxide, and bonding factors, 42:25 22156-157 [Rhp(C0)21P]2-,structure and bonding fac- electrochemical, areneiron complexes, tors, 4241 1399 [Rhio(C0)2J'l3~ organocobalt complexes, 11:432 structure and bonding factors, 4241 Reduction potentials, of conjugated hydro- synthesis, 42113 carbons [Rh,2(C0)27Sb]3-,synthesis, 42114 in 1,2-dimethoxyethane,2126 Rh4(cyclooctadiene)4(PPh)2, synthesis, 4280 in dioxane-water, 2121 Rhenium Reduction reactions, of organocopper com- binuclear octacarbonyldihydride, addition pounds, 12.253-254 to metal-metal double bond, 18230- Reductive acylation, k81-82 231,241 Reductive coupling, of aryl silanes, 15283 carbonyl halides, 815 Reductive coupling reactions, of transition clusters, 3578, 92 metal carbynes, 27933 mixed metal, 18213-214,232 Rhenium 268

triosmium, 2671 -72, 77-80 contraction of anions, 22:194 cyanocarbonyl anions, 1837-38 reaction with iodine, 22176 alkylation, 1840-41 triangular face-capping, 22182 binuclear, 1840 cdrbonyl halides, 8:239-240 n-cyclopentadienyl tricarbonyl deriva- carbonyl substitution mechanisms tives, 10:47-50 association in nitrosyl complex, 2k124 dimctallacyclobutadienes, 2699-100 CO dissociation rate parameters, halides, in olefin metathesis, 16284 2k117 hexacarbonyl cation derivatives, carbam- of pentacarbonyl radical, 2k143-144 oyl formation with amines, 1824-25 carbyne mixed alkali metal compounds, 22250 reactions with nucleophiles, 2270-71, pentacarbonyl anion, in redox condensa- 74-75,77 tion reactions, 18234-235 structure, 27:55 tetracarbonylmetallate(3-) anion, see Tet- synthesis, 2261-63, 69 racarbonylmetallate(3-) anion of cyclopentadienyl 0x0, 28361-362 manganese and rhenium cyclopentadienyltricarbonyl, 26150 Rhenium-carbon bond, 32176 decacarbonyl, see Decacarbonyldir- Rhenium carbonyl anionic derivatives, henium 2202 1,4-diaza-l,3-butadienes,2k160-161, acyl derivatives, 2208 176-178 binuclear anion, 2218 dienyl CdrbOnyl, 26366-369 hydride, 2205 dinuclear, W.178-179 with organic halide, 2207 p-ethylene, 20237, 242 preparation, 2:204 formate decarboxylation, 22140 sodium salt, 2203 gallium, 3%56 Rhenium carbonyl derivatives, 3:223-224 hydride, carbon dioxide insertion, 22138 ethylene complex, 349 isocyanides, 1157-58, 22222 halides, 3223-224 halides, 22233-244 Rhenium complexes protonation, 22:294 acyclic pentadienyltricarbonyl, isoelectronic, 30204-207 26:149-150 main group alkylidyne carbaborane, 31:83-84 bismuth, 31:137 anionic hydride gallium, indium, and thallium, spectroscopic properties, 27:4, 7-8, 21- 3k96-101 22,25 tellurium. 31:157-165 structure, 229-11, 17 nitrosyl clusters, a44 arene, 13:65, Yl carbide, 2451 bimetallic, 32224, 229, 232, 234. 239, 0-bridged lithium, 24437 244-245, 247,297 organolithium derivatives, M397-398 bis(,u-methylene)octacarbonyl, oxapentadienyl, 26:155 20186- 188 phenylethynyl, 38:123, 136 thermal stability, 20216 photochemistry boranes, 21:63-65, 82 nitrosyl cyclopentadienylalkylidenes, carbido carbonyl clusters. 2243-44 24338-339 carbide chemical shift, 2247 pentacarbonyl s-allyl, 24:291 heptanuclear trianion, 2243 trialkylbis (nitrile) derivatives, octanuclear dianion, 22:43-44 24291 -292 carbon dioxide, 22133, 135 q2-SiH, 30:170-172 carbon ylation, 11:125- 126 terminal C-C,O-bonded carbonyls carbonyl clusters with aluminum derivatives, 23238 269 Rhodium complex catalysts

with lanthanides, 23238 mixed-metal clusters, 18215-216, 219- with titanium tetrachloride, 23242, 220, 223-225, 239 294-295 and silane disproportionation, 19221 tricarbonyl halocyclopentadienyls, Rhodium, binuclear p-methylene com- 2k23-24 plexes trimetallic, 32246, 272-273, 298 carbonylcyclopentadienyls vinylidenes, 2264, 89, 100, 104-105 from alkylnitrosoureas, 20173-174 chiral nitrosyl, 22123 decarbonylation, 20177 Rhenium complexes, electron-transfer reac- isomerism, 20175 tions mass spectra, 20215-216 carbonyl phosphine halide isomerization, mechanism of formation, 20175-176 2320-21 MO calculations, 20197 carbonyls, 2318-19 protonation, 20223-227 of dinitrogen, 2322 synthesis, 20:175 isocyanides, 2322 thermal stability, 20216 mediation by CO ligands, 23294-295 with two methylene bridges, 20177, photoelectrochemistry, 2323-24 212 Rhenium formyl complexes, 206-8, 10-12, X-ray structures, 20178, 206-208 18 cyclooctadiene dimer, 20:250 alkylation, 2018-21 from ketenes, 20192-193 decomposition mechanism, 20:28-29 Rhodium carbidocarbonyl clusters, 2232- protonation, 2022 35, 38-43, 54 carbide chemical shift, 2247 reduction, 2024-25 effective radius of carbide, 2250 of aldehydes, 2016-17 with fifteen metal atoms, 2242 Rheniumpentacarbonyl alkyls, 32170-171 hexanuclear pentadecacarbonyl dianion, reactions, 32206-213 22:32-33 with cationic species, 32208 copper nitrile adduct, 2233-34 with Lewis acids, 32207 decarbonylation, 22:33-34 with nucleophiles, 32208-212 ferric ion oxidation, 22:39-41 orthometallation, 32207-208 NMR spectrum, 2246-47 with transition metal hydrides, 32206 structure, 22:33 synthesis, 32175-177 hexanuclear tridecacarbonyl dianion, Rhodium 2234-35 allyls, I3C NMR data, 19280-281, 283 octanuclear nonadecacarbonyl, 2240 diastereoisomerism, 19290-291 with twelve metal atoms, 2241 carbonyl anionic derivatives, 2234 Rhodium complex catalysts carbonyl cations, 8155-156 ethylene-butadiene codimerization, carbonyl halides, 3:243-244 12271-291 ethylene cyclopentadienyl complex, mechanism, 12272-275 349 ethylene glycol synthesis, 1280 phosphine complexes, 3243-244 use of carbonyl cluster, 1280 as catalyst in ethylene hydroformylation, Fischer-Tropsch reaction computer representation, 26199-201 use of carbonyl cluster, 17:75, 82 cyclopentadienyl(pentadieny1) cations, use of monomeric systems, 1285 26:152-153 hydroformylation, 124-53 hydrogenation catalysis, enantiomeric, hydrogenation 38180 asymmetric, 12338-356, 366-367 mixed alkali metal compounds, 22247- cationic diene complexes, 12328 248, 250 phosphine complexes, 17:321-333 Rhodium complex catalysts 270

supported complexes, 12361-367 hydrogen-bonded acceptors, 23241 hydrosilation, 12432-434 fluoroalkene, 3k188 methanol carbonylation, 17:255-267 hydndes and reduction of carbon diox- halocarbonyl anions, 12258-261 ide, 22:154-156 Rhodium complexes hydroformylation, 34:251-253 addition of acetylenes, 267 as hydroformylation catalysts, 16267-268 alkylidyne carbaborane, 3k61-63, 82-84 iminooxosulfuranes, 36:184-185 allenyl, 3283 isocyanides, 1k65-68 structure, 3288 oxidative addition reactions, 1k66 allyl, 32227 main group reaction with antimony and bismuth, 3k148-154 ethylene, 16245 tellurium, 3k167-168,172-173 sulfur dioxide, 16245 nitrido clusters, 24.63, 65,68-69, 74-76 u-n rearrangement, 16245 platinum derivatives, M63,68, 71-73 anionic hydride, spectroscopic properties, nitrosyl cluster, a62 27:s octafluorocycloocta-l,3,5,7-tetraene deriv- aqueous phase catalysis, 34260-261 ative arene, 1366, 111 cyclopentadienyl and indenyl, bimetallic, 32225-227,256, 262, 272 3k217-218 bis(ethylene)cyclopentadienyls, 2k11 dinuclear indenyl, 3k233-239 fluxionality, 2k11 pentamethylcyclopentadienyl, boranes, 2k63-64 3k225-229 carbido clusters, 24.75-76 perfluorobicyclo[3.3.O]octadienyl, carbon dioxide, 22132 3k230-233 carbonylation, 1k133-135 perfluorobicyclo[4.2.O]octatriene, carbonyl cluster rearrangements, 3k218-221 22198-199 perfluorobenzene, 3k199 carbonyl diazene, M89 perfluorocyclooctatrienediyl, 3k229-230 catalysis of olefin dimerization, 289-90, p henylet hynyl, 38126-127,134-135,137 199 photochemistry catalytic decomposition of formic acid, ammine ethyl cations, 24311-312 22140-141 rhodoximes, 24307 chiral Schiff base, 18200 (Ph3P)3RhCI, 269,85, 88 I3C NMR spectra, lN49 polynuclear species cyclooctadiene cyclopentadienyls, 2k12 heptanuclear, 16330 alkenyls, 2k45 hexanuclear, 16330 with halo substituents, 21:20 NMR spectral data, 16320-322 cyclopentadienyl, 8276-277 redistribution reactions as decarbonylation, reagent carbonyl phosphine halides, 2396, [RhCl(PPh,),], 1k111 107-111, 113 1,4-diaza-1,3-butadienes carbonyls, 23109,111, 115 bridged compounds, 2k166-167 phosphite, 23114 with chelate ligand, 2k160-161,181- sandwich, 37:304-305 184, 190 silyls, 1k258 dicarbonyl cyclopentadienyls, 2k9,11 in hydrosilylation, 1k305 bound to polymers, 21:48-51 sulfines, 36:176 nitro derivative, 2k29-30 sulfur dioxide insertion reactions, vinyl, 21:41-42 1267-68 edge-bridged 2-C,O-bonded carbonyls tertiary phosphine, 38179 with alkali metals, 23248-249 with thiazate ligands, 36:219 271 Ring-opening polymerization

tricarbonylmetallate(3-) anion, see Tricar- crystallographically characterized, bonylmetallate (3-) anion of rho- 3k338-339 dium and iridium dinuclear complex derivative trimethylenemethane protonation, 3k367 role in organic synthesis, 27:305-306 synthesis, 3k367-368 synthesis, 27:285-286 trinuclear, 3k366-367 vinylidenes, 2263, 123 fluxional behavior, 31:322-323 binuclear species, 2277, 82, 103, 109 high nuclearity water-gas shift catalysis, 34246-248 anticuboctahedral metal core, 3k370 Rhodium complexes, electron-transfer reac- heptanuclear, 3k371-372 tions octahedral anion synthesis, 3k367, 369 ally1 dimerization, 2337 synthesis, 3k304-305 cyclooctatetraenecyclopentadienyls, Rhodium(II1) TPTS complex, 38178 M97-98 Rhodium TPPMS complex, 38174-178 cyclopentadienyl carbonyls, 2358 Rhodium triphenylphosphine, 38176 fulvalene formation, 23:58-59 [Rh(PMe,)( 1)'-S=CPh2($CSHs)], synthesis, silver(1) adducts, 2359-60 43146 dienes, 2340-41 [Rh[P(OMe)3(~'-Se=CH2)(~s-CsMes)],syn- fulvalene derivatives, a94 thesis, 43153-154 ligand-bridged cyclopentadienyls, 24108 [Rh(PR3)(q1-S=CH2J($-CsHs)], synthesis, N-donor bridged dimers, 24123 43153 phosphines, 2330 Ribonuclease triphosphate, reduction by carbonyl halides, 2331-32 dithiols, 1k441 C-H bond activation, 2330 Ring-closure reactions, intramolecular, of hydrides, 2331 phosphine ligands, 15149-154 polynuclear carbonyl anions, a120 Ring closure via hydrosilation rhodocene derivatives, 2376-77 of acyloxysilanes, 12419 Rhodium complexes, as polymer-supported of alkenoxysilanes, 12418-419 catalysts, 15192, 224, 228-229 asymmetric, 12428 for hydroformylation, 15218-223 formation of disilacyclopentanes, 12418 for hydrogenation, 15206-209 mechanism, 12416 for hydrosilylation, 15214 of 4-pentenylsilanes, 12416 Rhodium dicyclopentadienyl, 1k236 Ring-coupled cyclohexadienyl complexes, Rhodium, high nuclearity carbonyl clusters, 1391 14:287 Rmg-exchange reactions, 32164 anionic species, 14329-332 Ring expansion reactions, 14328-332 in molybdenacyclobutadiene alkoxide structural studies, 14:288, 295-296, 298, complexes, 22336-337 302-305 in T~-C~H~~~.~.C~H~,4361-362 synthesis, 14328-332 via zinc carbenoids, 12:98-99 Rhodium hydride, 32226-227 Ring opening Rhodium isocyanides, 22219-220, 236-237 cyclosilanes, k105, 108-109 binuclear compounds, 22252-253, by insertion reactions, 5230 264-266 Ring-opening polymerization, 32132-133 homoleptic species, 22222-223 cyclic compounds, 32133 association, 22223, 248 cyclopentasilanes and cyclotetrasilanes, oxidative addition, 22260-261 3837-38 reaction with amines, 22292 [ l]ferrocenophanes photochemistry, 22257-259 germanium-bridged, 32151-153 Rhodium-platinum clusters phosphorus-bridged, 32153-160 Ring-opening polymerization 272

silcon-bridged, 32136-151 R2SnH2, dehydrocoupling for polymeriza- [2]ferrocenophanes, hydrocarbon- tion, 42385-386 bridged, 37:156-158 (R2SnX)n metathesis, 38170-171 NMR data, 33200 [2]ruthenocenophanes, hydrocarbon- structural data, 33198 bridged, 37:158-160 Rubidium [l]silaferrocenophanes, 32139-141 metal-carbon bond lengths, 43342-343 Ring opening reactions, of alkylidenecyclo- physical properties, 22174 propanes, 22283-285 safety in handling organometallic com- Ring strain pounds, 43269 cyclosilanes, 1:107, 137 solvation energy, 22182 and Grignard cyclization-cleavage re- structure determination of organometallic arrangements, 16:145-148 compounds, 43268,271-272,342 metallocenophanes, 32163 Rubidium, synthesis and structures of organ- Ring whizzers, 16:222-224 ornetallic compounds R2M=M'R2 compounds, structure and alkene derivatives, overview, 43309, 311, bonding 326 digermene, 33150-161 alkylalkoxide intermediates, 43291-292 structures and relative energies, 33:152 alkyl group exchange, 43:270 trans-bending, 33158-159 alkyne derivatives, 43:326 disilene, 33150-161 ally1 derivatives, 43:311-313, 315-319 arene derivatives, 43326-332, 334-341 small double bond dissociation energ- azaallyl derivatives, 43:319-320, 323-324 ies, 33158 azulene derivatives, 43307 structures and relative energies, 33151 benzyl and related derivatives, trans-bending, 33158-159 43:271-275 gerrnasilene, 33153-161 cumyl derivatives, 43275, 277 isomers of, 33155 cyclopentadienyl derivatives structures and relative energies, 33153 substituted derivatives, 43299-301, 304 trans-bending, 33158-159 unsubstituted derivatives, 43294-297, gerrnene, 33145-149 299 isomers of, 33146 fluorenyl derivatives. 0305-306 substituent effects. 33149 fuiierides, 43341-342 silene, 33143, 145-149 indenyl derivatives, 43.304 bond length, substituent effects on, methyl derivatives, 43271 33147 organolithium reagents, 43:269 isomcrs of, 33146 organomercury reagents, 43:269-270 methylsilene, energy differences be- pentalene derivatives, 43308 tween, 33149 phenyl derivatives, 43292-294 relative energies of, 33:148 silicon-substituted alkyl derivatives, RM-M'R compounds, structure and 43280, 283-286,288-289,291 bonding triphenylmethyl derivatives, 43277. 280 digermyne, 33161-165 Rubidium alurninate complexes, prepara- disilyne, 33161-165 tion, 4454 RzMg complexes, structural features, 32213 Rubidium, organometallic compounds, X- Roothaan-Hall equations, molecular orbital ray structural analysis, 22169-277 coefficient assignment, 42310-311 aggregation, 22180-18 I Rosenmund reaction, 4148 alkyls, 22191-192 Rotating-bomb calorimeter, 256 alkynyls, 22194 R2Si(H)O(CH2)nCMe=CH2,42392 bond lengths, 27:186, 190 273

bridging, 22177 reactions with gold-phosphine fragments, without carbon-metal interaction, 22239- 43107-110, 112 242,245,250,254-255, 257-258 stereochemical nonrigid behavior of clus- charge delocalization, 22173 ters, 43116-118 coordination, 22176 synthesis, 4345 cyclooctatetraene compounds, 22204 R~hC(C0)17 graphite intercalates, 22206-207 aggregation, 43101-102 ionicity, 22176 carbide ion origin, 4396-97, 99 mixed metal compounds, 22218-220, copper reagent reactions, 43112 231, 233 derivatives prepared from other clusters [Ru(C=CHC~H~-~-NO~)(PP~~)~(7’- pentaruthenium clusters, 4391-93, indenyl)]’, nonlinear optics, 42344, 346 95-96 [Ru( C ss CCbH4-4-(E) -CH =CHC6H4-4- triuthenium clusters, 4388-91 N02)(PPh,),( $-CsH5)], nonlinear op- electrochemistry, 43:48-49 tics, 42353-354 IR spectroscopy, 4346 [Ru(Ce CChH4-4-N02)( PPhT)2( $-CsH4R)], ligand reactions nonlinear optics, 42337, 353 alkyls, 4364 [RusC(C0),,]’-, condensation reactions, alkynes, 4364-65 43103-107 allyls, a69 [Ru&(CO)~~]~-,synthesis, 43101 arenes, 4375, 77, 79-86 [RU~~C~(CO)~~]*-,synthesis and structure, cyclobutadienes, &71-72 43:100-101 cycloheptatrienyls, 4386 RusC(CO)IS cyclopentadienyls, 4372-73 copper reagent reactions, 43112 fulvenes, 4373 derivatives prepared from other clusters hydrides and halides, 4349-50 pentaruthenium clusters, 4391-93, nitrogen donors, 4350, 53 95-96 oxygen donors, 4359 triuthenium clusters, 4388-91 phosphorous donors, 4353-59 electrochemistry, 4348-49 selenium donors, 4360-61 IR spectroscopy, 4346 sulfur donors, 4359-62 ligand reactions mercury reagent reactions, 43112 alkyls, 4364 nuclear magnetic spectroscopy, 4346 alkynes, 4364-65 reactions resulting in higher nuclearity allyls, 43:69 clusters, 4399-102 arenes, 4375, 77, 79-86 solid-state structure, 43:46-48 cyclobutadienes, 4371-72 stereochemical nonrigid behavior of clus- cycloheptatrienyls, 4386 ters, 43116-118 cyclopentadienyls, 4372-73 synthesis, 4344-45, 88 fulvenes, 4373 RU~C(CO)~~{AU~(P~ZPCH~)~],synthesis, hydrides and halides, 4349-50 and structure, 43108-109 nitrogen donors, 4350, 53 RU~C(CO)~~(AU~(P~~PCH~)~),synthesis, oxygen donors, 4359 43109 phosphorus donors, 4353-59 RusC(CO),,(AUPP~~)(~-X),synthesis and pyridine, 43:86-87 structure, 43107 selenium donors, 4360-61 RuSC(CO),,(AuPPh3)X, synthesis and struc- sulfur donors, 4359-62 ture, 43107 mercury reagent reactions, 43112 RU~C(CO)~~(AUPR~)~,synthesis, 43108 nuclear magnetic spectroscopy, 4346 RusC(CO) 14(A~PR3)2.synthesis, 43108 reactions resulting in higher nuclearity Ru&( CO) 6( AUP~~)~,synthesis, 43109 clusters, 4399-102 Ru~C(CO)~~(C~H~M~)~,synthesis, 4383 274

Ru,,C(C0)11(CbH3Me)2,stereochemicalnon- [RU6c(co),,(p-BT)]z, synthesis, 4350 rigid behavior, 43117 Ru5C(CO)lI(~-Br)*(l*.-CIHs)(q-C-rHs), syn- Ru,C(CO),,(COMe)], synthesis, 4364 thesis and structure, 4369 RusC(CO)l-r(dppe),synthesis and structure, [Ru~C(CO)~~(~-C~H~)],synthesis, 4369 4355 RkC(CO)i 1 (p"-C&-1,4)2 Ru,C(CO),,(dppf), synthesis, 4358 stereochemical nonrigid behavior, Ru6C(CO),,( q-arene)( q-CsHh), synthesis, 43116-117 4382 synthesis and structure, 4375, 77 Ru6C(CO)11(q-arene)(p3-C6H6), synthesis, RusC(CO)I~(PL~-C&) 4382 stereochemical nonrigid behavior, 43117 RU~C(CO),~(?)-arene)(p-cd&), synthesis, synthesis and structure, 4377, 79 4381-82 RU~C(C0)13(p-C&), synthesis, Kk75 RU&(CO),~(q-arene)(p&Mez). synthesis, Ru~C(CO)~~(~,-C~H~.~,~),synthesis, 4375 4384-85 Ru6C(CO)14[p3-C14H14),synthesis, 4386 RubC(CO),,( q-arene) synthesis and struc- RU~C(CO)~,(~~-C,H,),synthesis, 4380 ture, 4390 RU~C(C~)~~(~~-C~H,~),synthesis, 4389-90 Ru~C(CO)~,(~~-C,H,)~,synthesis and struc- RU~C(CO),~(~-GH~),synthesis and struc- ture, 4379 ture, 43:99-100 RU~C(CO)~,(q-C6H6), synthesis and struc- RU~C(CO)~~(~~-C~~H~~),synthesis and struc- ture, 077-79 ture, 4399-100 Ru~C(CO),~(q-C6Hh), synthesis and struc- RU~C(CO)~~(~-C~H~CC[CH~)~~synthesis, ture, 4379 4373 Ru6C(CO),I(q-ChH6)2, synthesis, 4384 Ru&( CO) 4( p-CH2(CH)4CH2}, synthesis, Ru,C(CO),,( T-C~H~)~,synthesis and struc- 43.84 ture, 4373 Ru6C(C0),,,[p3-CSH4CMe2),stereochemical Ru5C(CO),,(q-CSHs) (AuPR3), synthesis, nonrigid behavior, 43117 0110 RU~C(CO),~(~~-(CHCO~M~)~),synthesis [Ru~C(CO)I~(~-C~H~)(~~-C~H,)[BF~I,s~n- and structure, 4387-88 thesis, 080-81 RU~C(CO)~~[~~-C~H~(CO~M~)~-~,4], synthe- Ru&(CO) 12( q-C6H6(pCgHs),synthesis and sis, 084 structure, 4380 Ru6C(CO) I4[ p-C5H4CPh2),stereochemical Ru6C(CO), ( ~-C~H~)(~TGH,)synthesis , nonrigid behavior, 43117 and structure, 4373 Ru6C(CO),,[ p3-CSH4CPh2),synthesis and Ru6C(CO)I ,( q-C6H3Me2-1,3J2, synthesis, structure, 4373 4383 RU~C(CO)~,(q-C6H3Mel-lr3,5)2. synthesis, Ru&( CO) 1 S[ p-CsH4CPhZ),synthesis and 4382-83 structure, 4373 Ru,C(CO),~(T-CSH4PPh3), synthesis, 4373 RU6C(C0)15(p,-Cl,H~~-p-o),synthesis and RU~C(CO)~~(~-C~P~~),synthesis and struc- structure, 4397, 99 ture, 4371-72 Ru~C(CO)~~(~-C~)(H~CI),synthesis, 43112 RU~C(CO),~(~-C~P~~),synthesis and struc- RU&(CO)~2(p3-C2Me2)1, synthesis, 4365 ture, 071-72 Ru,C(CO)&,-C~M~~)~,synthesis, 4365 [ Ru6C(CO)lo( HgCF3)]-,synthesis, 43112 Ru~C(CO)~~(~~-~M~~),synthesis, 4365 RusC(CO) s(HgCF3)(OCOCF3), synthesis, RU&(CO)~~{~-CNM~~)~,synthesis and 43112 structure, 4391 Ru&(CO),~(~'-~S~),synthesis, 4362 RU~C(CO),,[~-(C,O,M~)~],synthesis and [Ru,C(CO),,I,]-. synthesis, 43101 structure, 4388 [RU~&(CO)~~I]-,synthesis, 43101 [RU,~C~(CO)~~(~~-C~P~~)]~~,synthesis and [RuFC(CO),J(p-I)(p-COMe)]-, synthesis structure, 43101 and structure, 4388 RU,C(CO),~(~~-C~P~~)~,synthesis, 4364 275 Ru,PtC(CO),,

R&C( C0)14(p-CZPhZ)(p3-C2Me2)rsynthesis, RuC13,preparation of $-arene rutheni- 4365 um(I1) complexes, 29164-165 Ru&(CO)&-dppf), synthesis, 4358 [RuC1( C= CC6H4-4-C6H4-4-N02)(dppm )2], Ru6C(CO)16(Me)-, synthesis, 4364 nonlinear optics, 42354 Ru5C(C0)&-$-COMe)(AuPPh3), synthe- [RU3(CO)I*l sis, 43110 adsorption on y-A1203,32143 Ru5C(C0)13(p-q2-N02)( q-C3Hs), synthesis catalytic activity of, 32:129-130 and structure, 4369 cocatalysis, 32131 Ru5C(CO)I I(p-73-12S3), synthesis and struc- mixtures, analysis of, 32129 ture, 4361-62 phosphorus ligand, addition of, 32130 RusC(CO)13(p-v1-12S3), synthesis and struc- potassium hydroxide, 32136 ture, 4361-62 rhodium phosphine system, 32131 Ru6C(CO),,(p-$-12S3), synthesis, 4362 selectivity, 32129-130 Ru~C(CO)~~(~-$-~~S~),synthesis, 43:62 RU~(CO)~~B~~,structure and bonding fac- Ru~C(CO)I~(~~-$-SCH~CH~SCH~CHZS), tors, 4247 synthesis, 4362 Ru3(CO)8( C6H4Cr( CO)3](PtBu), synthesis, Ru6C(CO)&-MeCH=CHCH=CHMe), 4291 synthesis and structure, 4388-89 Rus(C0)16(p-PPh2)(pS-P),structure and Ru5C(CO)14(p-NO)(p-$-N02), synthesis, bonding factors, 4239 43:53 Ru3(C0)9(NAr)2,synthesis, 42123 RUSC(C0)i 1 (~-NO)(~-$-N~Z)(~-C~HS),RU~(CO)~~(NCO)N, structure and bonding synthesis and structure, 4369 factors, 4238 RU~C(CO)~~(~-NO)(EL-~-NO~)(PP~~),syn- RU~(CO)~~(NP~), synthesis, 42122 thesis, 43.53 [R~(C0)3(PPh3)2],32122-123, 140-142 RU~C(CO)~~(~-PE~~)~,synthesis, 4391 Ru4(CO)13PPh,structure and bonding fac- Ru6C(C0)&-PEt2)( q-CsH5),synthesis, tors, 4223 4391 Rus(C0)15PR, synthesis, 42109 RU~C~(CO)~~(~-PP~~)~,synthesis and struc- [RU~C~C(CO)~~]~-,synthesis, &lo4 ture, a100 [RU~CU~C(CO)~~(NCM~)~],synthesis, Ru6C(CO)lo(p-PPh2)2(~3-CH)h-C~H~-Mex), 43112 synthesis and structures, 4395-96 [Ru(EDTA)(HzO)I Ru~C(CO),~(p-PPh2)(p-PPh2C3H3Me), syn- carbonylation, 32126-127 thesis and structure, &92 catalytic cycle, 32127 RU~C(CO)~~(~-S~P~)~,synthesis, a60 dihydrogen heterocyclic activation of, Ru6C(C0)1s(p-SePh)-,synthesis, 4359-60 32126 Ru6C(CO)&-SePh)(AuPPh3), synthesis, RusFeC(C0)13(7-PPhz)2,synthesis, 43116 43109-110 Ru5Fe3C2(C0)17(p-PPh2)2,synthesis, a116 RU~C(CO),~(NCM~)~,synthesis, 4350, 53 RU~(~-EL~-CO)~(CO)~~(~-C~H~M~~-~,3,5), Ru,C(CO),,(NO)~, synthesis, 4353 synthesis and structure, 4396 Ru~C(CO),~(NO)(AUPP~~),synthesis, RU~MC(CO)~~(AUPE~~)~,synthesis, &110 43109 [RU~MOC(CO)~~]~-,synthesis, 43104 Ru5C(CO),,(NO)(AuPr3), synthesis, a109 Ru4MozC(p-O)(CO)12(v-CsHS)2,synthesis, RU~C(CO)~~(P~~P(CH~)~PP~~),synthesis, 43116 4357 [Ru2(00CR)4X], 32132 RU~C(CO)~~(PP~~),synthesis, 4353-54 rutheniudphosphonium salt system, RU~C(CO)~~(PP~~)(AUPP~~)(~-I),synthesis 32134 and structure, 43107-108 supported catalysis, 32140-143 Ru6C(CO)16(PPhzEt),synthesis and struc- RU(PP~~)~($-C,H,),nonlinear optics, ture, 4357 42336 RU~C(CO)~~(PP~~H),synthesis, &56 RuSPtC(C0)16,synthesis, a105 276

RU,P~C(CO)~~(q4-C8HI2-1 3, synthesis, phenyl acetylene, a43 43104-105 ruthenium acetylide, 3032 Ru~P~~C(CO)~~(~~-C~H~~-~,5)2, synthesis, vinylidene interconversion, 3042-43 43105 preparative route, M42 [RuiRhC(CO)14(q4-C8H12-l,5)]-, synthesis Ruthenium, d'-alkylidene complexes, syn- and structure, 43106 thesis, 25159-161 Ru5RhC(CO) 14( T$C~H,~)(AUPR~),synthe- from carbyne complexes, 25159-160 sis, 43110 from hydroxy-, alkoxy-, and halomethyl RU~R~C(CO),~(~-C~M~~),synthesis and complexes, 25160-161 structure, 43106 Ruthenium, d'-alkylidene complexes, syn- Ru~RhC(CO)lg(rl-CSMes)(q-CsHs)synthe- thesis, 25156-159 sis and structure, 43105-106 alkylidene formation mechanism, Ru5RhC(CO)14(q-CsMes)synthesis and 25158-159 structure, 43:105 diazoalkane route, 25156 Ruthenaboranes, 29191 reactions with OsCI(NO)(PPh3)3, Ruthenacarboranes, 29190 25156-157 Ruthenacyclophane complex, 29223 reactions with other substrate complexes, Ruthenium 25157-158 carbamoyl compounds, 1829-30 Ruthenium, allenylidene complex, cyclopen- carbonyl in phase transfer, catalysis, tadienyl bisphosphine 19187-188 geometry, a63-64 nitrobenzene reduction, 19187-188 resonance form, 3063-64 high nuclearity carbonyl clusters, 14287 structure, 3063 structural studies, 14288, 293 preparation, 3059-63 synthesis, 14324 cyclic propargyl alcohol, 3060-62 mixed alkali metal compounds, 22209- 1,l-diphenylpropargyl alcohol, 210, 251 3059-60 mixed-metal clusters, 18212, 214-222 Ruthenium, anionic hydride complexes via pyrolysis reaction of dodecacarbo- as catalyst, 2245 nyl, 18229-230 reactions N-, 0-,S-, and Se-substituted carbene with alkyl halides, 2236-37 complexes, range of, summary, with Brgnsted acids, 2233 25142- 146 spectroscopic properties, 275, 8, 21, 23 "C NMR spcctra structural properties, 2218 ~3-allybis(phosphine),19298-299 Ruthenium, carbene complexes q'~allyls,19266-267 bonding models, 25123-125 q4- butadienetricarbonyl, 19275 carbene fragment, 25123 organogallium compounds, 3948, 52 charge distributions, 25124 polynuclear compounds with bridging C7 coordination to metal, 25123-124 rings, 19179 geometries, 25124-125 Ruthenium, acetylide complex, cyclopenta- substituent effect, 25124 dienyl bisphosphine reactivity patterns, 25125-129 cycloaddition, 3058-59 effect of metal basicity, 25127-128 alkene, 3058-59 reactions with nucleophiles, 25126-127 geometry, 3032-34 Ruthenium, carbene complexes, cyclopenta- steric constraint, 3032-33 dienyl bisphosphine structure, 3033-34 cyclic, 3051-52 preparation geometry, 3054-55 copper(1) phenylacetylide, 3031-32 steric constraint, 3054-55 lithium phenylacetylide, 3031 structure, 3054 277 Ruthenium complex catalysts

preparation, 3048-54 with nucleophiles, 22176 acetylenic alcohol, 3051 triangular face-capping, 22183, 191 5-chloropent-l-yne, 3052-53 Ruthenium, carbonyl diazene complexes ethyne, 3049-50 internuclear carbonyl scrambling, 3479 vinylidene, 3048-51 metal induced bond cleavages, 3493, 97 reaction preparation, 34:78 deprotonation, 3056-58 tetranuclear cluster, 3479 lithium aluminum hydride, 3056 Ruthenium carbonyl [RU~(CO)~~],neutron substituted sodium aluminum hydride, irradiation, 1k229 3055 Ruthenium, carbyne complexes Ruthenium carbidocarbonyl clusters bonding models, 25129-131 anionic thallium derivative, 2228 carbene fragment, 25129-130 carbide chemical shifts, 2247 charge, 25131 effective radius of carbide, 2250 heteroatomic substituents, 25130 hexanuclear heptadecacarbonyl, 2217,21 substituent effects, 23130-131 alkyne derivative, 2224-25 varying metal fragment, 25131 arene derivatives, 22:21-22 cationic d8 complexes, 25184-185 bitropyl derivative, 2224-25 I3C NMR spectroscopy, 25188 carbonylation, 2217 coupling reactions, 2285 hexadiene derivative, 2226 a-metalladiazoalkanes as precursors, phosphine substitution, 2224 25183-184 reaction with ethanethiol, 2226-27 modification of existing carbyne com- structure, 2222 plexes, 25184-186 synthesis, 2222 modification of existing ligands, hexanuclear hexadecacarbonyl dianion, 25182-184 2223-27 oxidation of metal by iodine, 25186 copper nitrile adduct, 2226-27 oxidation of metal by oxygen, 25185 I3C NMR spectrum, 2247-48 reactivity patterns, 25131-134 oxidation, 2224 electrophilic addition, 25133-134 protonation, 2223 nucleophilic addition, 25131-133 structure, 2223 synthesis, 25181-186 and tropylium bromide, 2224-25 from dihalogenocarbenes, 25182-183 pentanuclear pentadecacarbonyl, 2217 vibrational spectroscopy, 25188-189 anionic halide adduct, 2219 Ruthenium-chloride, as catalyst, 38170 reactions, 2217-19, 184 Ruthenium clusters, see Transition metal Ruthenium-carbon bond, 3888-89, 104, 114 clusters Ruthenium carbonyl Ruthenium complex catalysts anion, 2218 Fischer-Tropsch reaction, 1275-79 and cleavage of C-H and C-C bonds, alkane formation, 1275 12369 product distribution, 1278 Lewis base complexes, 3235-236 reaction rates, 1276-77 Ruthenium carbonyl clusters selectivity, 1275 as catalysts use of capping ligands in clusters, carbon dioxide reaction with hydrosi- 1277-79 lanes, 22163 hydroformylation, 1253-55 formic acid decomposition, 22141 as hydrogenase models, 12380-381 methyl formate formation, 22158-159 asymmetric, 12356-357 nitrene, 22182 of DIOP, 12356-357 reactions on support, 12365 with alkynes, 22185 shift reaction, use of carbonyl, 1284-85 Ruthenium complexes 278

Ruthenium complexes edge-bridged X-C,O-bonded carbonyls acyclic pentadienyl, 26:137-138,140, with alkali metals, 23248 154-155 alkylated clusters, 23250 alkyl, 38108 with aluminum derivatives, 23251,253 alkylidene carbaborane, 31:63-64,68 hydride clusters, 23:246 p-alkylidenes, 20188,248-249 p-ethylidyne, 20188 alkynyl, 38104-105,108, 110-111, 114, face-bridged Z-C,O-bonded acyl cluster, 117 23266 allenyl, 3266-124 fluxional cyclooctatetraene complex, aqueous phase catalysis, 34:259-260 16217 arene, 1365-66,79,93-94,102-104, NMR studies, 16217-218 107-111 formyls, 207,10 benzyne, synthesis, 42168 fullerenes, 3674 bimetallic, 32228-229,232, 234-235, 238, hydroformylation, 34253 244,280,282,285, 289-291 iminooxosulfuranes, 36183-184 borane, 21:63-64,29:190-191 main group carbonylation, 1k130 antimony and bismuth, 3k139-147 carbonyl diazirine, 3480,97-98 tellurium, 3k165-167,172 chiral arene, 18199 thallium, 31:105 circular dichroism, 18193 p-meth ylenedicarbonylcyclopentadienyls, of optically active aminophosphine, 20248 18192-193 thermolysis, 20249 chlorocyclopentadienyl, 2k25 X-ray structure, 20249 clusters, M234 tris(p-methylene)hexakis(trimethyl- and CO reduction, 23290 phosphine), 20192 hydride carbonyl rearrangement, in hydrogenation catalysis, 20223 16333-334 protonation, 20:224-225 NMR spectral data, 16320-323 mononuclear, synthesis, 29:235-237 cyclopentadienyl arenes, 2375 nitrido clusters, 2445,64, 66-67, 70-71, ruthenocenes, 23:70-71, 79 74-76.78,80 cyclopentadienyl bisphosphine auxiliary, with cobalt, 2465 301-76 cyanate derivative, 24230-81 acetylide, 3031-34,58-59 with iron, 2456,68, 70-71, 73,75-80 allenylidene, 3059-63 nitrosyl carbonyl anion, 24:47, 55 carbene, 3048-58 nitrosyl clusters, 2442-43,46, 50, 52-54, disubstituted vinylidene, 3043-48 57-61, 67-69 T2-unsaturated ligand, 3066-68 carbide, 2446-47,52-53 vinylidene, 3034-42,58-59 with iron, 2447-48,56-57 1,4-diaza-l,3-butadienes olefin metathesis via chloride, 16284 binuclear carbonyls, 2k158,162-163, with organosilicon ligands, 1k257 193-203 pentacarbomethoxycyclopentadienyls, with chelated ligand, 2k160-161, 2k17-18 178-181 pentalene molecular rearrangements, fluxionality, 2k210-212 16340-341 ligand activation, 21:225-233 phenylethynyl, 38124-125, 136 substituent effects, 2k205-207 photochemistry dinitrogen, 16272 binuclear alkylidenecyclopentadienyls, dodecacarbonyl nonrigidity, 16:328 2k339-340 double-layered, cyclic voltammetry, bis(carbene)-bridged cyclopentadienyls, 29:224, 226-227 24340 279 Ruthenium

dicarbonyl cyclopentadienylalkyls, nitrogen ligand modified, 32135 24295-297 [N(PPh3)2] [HRu~(CO)131, 32132-133 polymetallic derivatives and, 29:229-235 phosphorus ligand modified, 32135 silene, 3988 photochemical activation, 32:140 silyl-substituted cyclic polyolefins, polynuclear compounds, 32130 15132-137 reductive dianionic species, 32133-134 sulfur diimides, %215 Ruthenium, dihalo- and monohalocarbene trimetallic, 32246 complexes trimethylenemethane metal-carbon bond, 25173 role in organic synthesis, 22306 metallacycle formation, 25179-180 synthesis, 27:285 migratory insertion reactions, 25180 p-vinylcarbenes, 20:219 reactions with p-vinylidenes, 20188-189 electrophiles, 25180 protonation, 20188 nucleophiles, 25176-179 water-gas shift catalysis, M249-250 structure Ruthenium complexes, electron-transfer re- carbene ligand orientation, 25175 actions carbon-halogen bond, 25173-174 and activation of small hydrocarbon I3C NMR, 25175 bridges, 24123 IR spectroscopy, 25175-176 $-allyl, 23:37 metal-carbon bond, 25173 aryl, 2335 trans influence, 25175 bis(arenes), 2375 Ruthenium, dihalocarbene complexes, syn- carbonyl phosphines, 23:27 thesis cyclobutadiene derivatives, 2339 cyclopentadienyl alkyls, 2355 cation generation for CC12 with silver iron metallocenophane, 24:92 salts, 25171 ligand-bridged cyclopentadienyls, M105 CC12 complexes from reactions with trinuclear carbonyls, 24:112, 116, 124 Hg(CC13)2, 25170-171 Ruthenium complexes, reactions conversion of CClz complex to CFCl com- background, 32121-122 plex, 25171 [(V~-CSHS)RU(CO)~IZ modification of a-dihalocarbene ligand analgous iron complex, comparison to, containing complex, 25171 32134 modification of trihalomethyl derivatives, breakdown products, 32125 Ln-CX3,25169-170 isomerization vs. monomeric species, Ruthenium isocyanides, 22216,219-220, 32126 234-235,245-246 mechanism, 32125 arenes, 22234 [($-C~H~)RU(CO)~X],32125-126 clusters, 22229, 231 cluster catalysis cyclopentadienyls, 22241 anionic species, 32132-137 dimeric species, 22220,222,235-236,245 mechanistic studies, 32137-139 halides, 22234-235 neutral species, 32129-132 reaction with amines, 22292 dimeric vs. monomeric, 32122, 126 Ruthenium, monohalocarbene complexes, dinuclear bridged, 32137 synthesis [(EDTA)RuCl], 32127-128 modification of a-dihaloalkyl derivatives, [HRh(CO)(PPhS)?], 32122 LnM-CX2R, 25171-172 [HRu,(CO),,], 32137-139, 142 modification of carbyne complexes, hydroformylation, 32122-128 25172 K[Ru(EDTA-H)Cl]2H20,32128 modification of monohalocarbene ligand- monoanionic complexes, 32134 containing complex, 25172 Ruthenium 280

oxidative addition of [Me2NCC12]C1, steric constraint, 3068 25172 Ruthenium, vinylidene complex, cyclopenta- Ruthenium, nonheteroatom-substituted car- dienyl bisphosphine bene (alkylidene) complexes acetylide interconversion, 3042-43 carbene ligand conformation, 25163 alumina, 3042 chalcoformaldehyde complex reactions, cycloaddition reaction, 3058-59 25166 oxygen, 3058-59 electrophilic addition reactions, disubstituted, 3043-48 25: 164-1 66 carbon disulfide, 3046-47 gold adduct reactions, 25166 cyclization, W44-45 halomethyl ligands as methylene precur- diazomethane, M45-46 sors, 25167 ruthenium acetylide, 3044-45, 47-48 metal-carbon bond of, 25:162-163 geometry, 3038-42 nucleophilic addition to Os(=CH,) dynamic NMR, 30:41-42 CI(NO)(PPh,)l, 25167-168 Fenske-Hall calculation, 3038 reactions with halogens, 25167 71 interaction, 3040 spectroscopic properties, 25163-164 rotamer, 3042 structure, 25161-164 structure, 3039-41 sulfene complex reactions, 25166 mechanism, formation, 3035-38 synthesis Hiickel calculation, 3035-36 dx-alkylidene complexes, 25156 1,2-hydride shift, 30:36-37 reactions with OsCI(NO)(PPh,),, insertion, 30:37-38 25156-157 intermolecular, M37 trans influence, 25163 preparation, 3034-35 Ruthenium-platinum clusters alkyne, 3034 crystallographically characterized, 3k332 stereospecificity, M35 fluxional behavior, 31:320, 323-325 water reaction, 3052 high nuclearity, 3k348-350 Ruthenium vinylidenes, 221 14-115 tetranuclear binuclear cyclopentadienyls, 2279-80, preparation, 31348 109, 112 reaction, 3k348-350 protonation, 2281 trinuclear, 3k346-348 carbonyl clusters, 221 15-116, 122 axially bound phosphine, 3k347 with gold, 22119, 122 preparation, 3k346 with nickel, 22120-122 steric factor, 3k347 cationic cyclopentadienyls, 2264, 100, tungsten species, 3k382-383 106-107 Ruthenium propadienylidenes, 2283, 101, ligand transfer, 221 12-113 110 reaction with alcohols, 2270 clusters, 22121 reaction with oxygen, 2275 Ruthenium tetraoxide, 29190 Ruthenocene, 2378, 8271, 26:140 Ruthenium-TPPMS complexes, 38:175 from ferrocene Ruthenium-TPPTS complexes, 38178 and RuCI,, 1094 Ruthenium trichloride, 29:190 and uranium fission reactions, 1k237 Ruthenium( 11)-tertiary phosphine complex, neutron irradiation, 1k224 38179 [l]Ruthenocenophanes, 32162-163 Ruthenium T2-unsaturated ligand complex, [2]Ruthenocenophanes, hydrocarbon- cyclopentadienyl bisphosphine ethylene bridged, ring-opening polymerization, preparation, 3066-67 37958-160 alkyne, 3066-67 Ruthenocenyl carbyne complexes, 32291 double-bonded species, 3066-67 a-bond metathesis reaction, 3246 28 1 complexes

a-aligands, in bimetallic and trimetallic s-block elements, terphenyl derivatives, complexes, 32219-310 U6-9 Ruthenocenyl complexes, third-order non- Sb metallacycles, synthesis, 42157 linear optics, 43368-370 [Sb7Ni3(C0)313- Ruthenocenyl group, electron donor proper- structure and bonding factors, 42:73 ties, 10110 synthesis, 4288 Ruthinaindane, stability, 42165 Scavengers, in radiochemical reactions, [RU~WC(CO)~,]*-,synthesis, 43104 1k246 Ru4WC(CO)12( v-CsHS) (w-CPh), synthesis SCHAKAL plot, 36244 and structure, 43115 Scheller reaction, 4151 RusWC(CO)14(~-C5Hs)(p-CPh),synthesis Schiff base complexes, 10:154 and structure, 43115 fragmentation pattern, 6:295 ortho-metallated, 10:157 Schiff bases S chiral metal complexes Group VI metal tricarbonyl phos- Salicylaldehyde, reaction with organoplati- phines, 18162-163, 196 num compounds, 22118 manganese tricarbonylbromide, 18163, Salicylato(2-) bidentate ligand, in spiro- 196 cyclic k%i-silicates molybdenum cyclopentadienyls, NMR studies, 44.254 18:164-165, 177-179, 195, 197 synthesis, a252 cocyclization with butadiene, 12178 X-ray diffraction analysis, 44:252-254 hydrogenation of imine group Salts asymmetric, 12353-354 molten, in hydrogenation catalysis, 12368 by rhodium phosphine catalyst, 12325 organic, carbene complex synthesis from, organo-cobalt complexes, 11:376-381 25141-142 palladium and nickel complexes as hydro- Samarium genation catalysts, 12387 dicyclopentadienide, 9379-380 reduction via hydrosilation, 12338 indenyl compound, 9376-377 Schlenk equilibrium, 4283-285 Samarium complexes Schomaker-Stevenson equation, 38106 acetylide-bridged bis(cyclopentadienyl), Schonflies notation, k245-246 24:139-140 Schrock-type alkylidyne-metal complexes, bis(pentamethylcyclopentadieny1) deriva- 35:139-140 tives, 24:161, 167-171 Scrambling equilibria, silicon systems, 6:228 in catalyzed hydrogenation, 24:168-169 Second harmonic generation, measurement ligand-bridged dimers, 24.168-169 of organometallic second-order nonlin- via oxidative addition to metal, 24.167 ear optical properties reaction with alkynes, 24:169 crystals and films, 42303-304 samarocene, 24171 electric-field-induced technique, divalent cyclopentadienyls, 24158 42304-305 homoleptic tertiarybutyl anion, 24137 Kurtz powder technique, 42301-303, Sandmeyer reaction, a305 315, 318-319, 321,324 Sandorfy C method, 34:176 Selection rules, k242-243, 248, 294, 296 Sandwich structure Selective excitation, and DANTE, r-ally1 metal complex, 2330-331 2&422-423 ferrocene, k240-241 Selectivity control, in nickel-catalyzed olefin [Sb2C04(C0),J, structure and bonding fac- oligomerization, 1R105-137 tors, 4250-51 Selenadigermiranes, 39:302 SbFe,(C0)9(CH), synthesis, 42108 Selenide complexes, reactions Selenide complexes 282

diazo compounds, 3297 ligand substitution and atom ab- insertion straction acetylenes, 3299-101 associative substitutions, 40:183-184, ethene, 32:99-101 187- 188 synthesis electrocatalytic substitution, methylene addition, 3296 40C188-189 selenoformaldehyde complexes, 3296 electrochemical current efficiencies, Selenium 40.188 biomethylation, 20327-328 oxidation and enhancement of ligand mechanism, 20339 substitution, 40191 mixed alkali metal compounds, oxidation waves, &185-187 22228-229 photosubstitution reactions, ?i complexes, 26:285-286 40:191-192 reaction with tetracarhonyls, 29141-142 relative reactivities, 40:192-193 terphenyl derivatives, 4455-56 ring slippage, 40:187-188 Selenium dioxide, 36d66-167 steric effects, &187 Selenium-silene adducts, 39:132 stability range, M172-173 Selenium-substituted carbene complexes redox-induced isomerizations, 40205-207 reactivity redox switches, 40.207-209 carbene ligand rearrangement, 25:lSS synthesis nucleophilic substitution reactions at chemical oxidation, 40175 a175 Ca, 25149-153 electrochemical oxidation, 40:175-176 oxidative addition reactions, electron transfer, 25154- 155 hydrogen atom extraction from eigh- teen-electron metal hydndes, spectroscopic properties, 25149 40.174 structure, 25146-148 photolytic cleavage of metal bonded di- synthesis, 25135-146 mers, &174, 193 Selenium trioxide, insertion reactions, 5293 reduction of eighteen-electron precur- Selenoaldehyde compounds, see Heteroalde- sors, 40:176 hyde transition metal complexes types, 40:172-173 3221-23 Selenocarbenes, Sex hormones Selenocarbonyl compounds, see Heteroket- effect of polysiloxanes, 18289 one transition metal complexes silylation and activity, 18283-285 Selenocyanate complexes, 10180 S-H bond, coordinated, ketene cycloaddi- Selenocyanates, see also Pseudohalides tion reaction and, 28:lO properties, 5218-219 Shift reaction, homogeneous catalysis, Selenolates, multiple bonding, 3944-47 17~83-86 Semiconductors, 3869-70 Siberg silene, properties, 3994-95 o-Semidine derivatives, 10136 Sic, synthesis by dehydrocoupling, 42383 Seventeen-electron organometallic radicals Sidgwick effective atomic number, 1:177 acidity of cation radicals, a177 h5Si-fluorosilicates migratory insertion geometry, 44:224-225 alkyl to acyl migration, 40:204 isolation, 44:224 equilibrium constant for carbonyl inser- Sigma-bonded groups, as ligands, 2&299- tion, &203 301, see also specific sigma-bonded hydride migration, 40204 groups reactivity Sigmatropic rearrangements, in organo- comparison to eighteen-electron radi- boron compounds, 1672-82 cals, &171, 173, 190 $-SiH complex 283 Silanitrile

bonding, 30:151-154 l-Silacyclopent-3-enes, 39145 evidence, 30155-162 Silacyclopropane, 39251 theoretical interpretation, 30162-164 silyene-Lewis base complex synthesis, tuning, M164-170 4331-32,36 chromium, 30:172-173 via silylene addition to C=C bonds, comparison, hZ-CH, 30182-184 1963-67 dinuclear metal, bridging M-H-Si, alkenyl derivatives, 1968-69 30:174-179 photochemical isomerization, 1966 platinum, 30177-178 Silacyclopropanimines, 39219 rhenium, 30178-179 Silacyclopropene, B70-72, 39144 titanium, 30174-177 methanolysis, 1970 tungsten, 30178-179 palladium-catalyzed dimerization, dynamic behavior, 30:18 1-1 82 19216-217 four-legged piano stool, 30180-182 via photolysis of alkynyldisilenes, isoelectronic, 30207-208 1988-92 manganese, 30154-170 1,2-hydrogen shifts, 1989 NMR measurement, 30157-158 Sila-enolate, 3821-22 photoelectron spectra, 30:163-164 Silaethenes, 39159 rhenium, 30170-171 Silaethylene tungsten, 30178 MO calculations, 21:277 1,4-(SiH,),(Si,Melo), dehydrocoupling for properties, 39100 polymerization, 42382 [l]Silaferrocenophanes, 32154 Silaallene, 3988, 131, 141, 144 dimerization, 32163 and isomers, calculations on, 2522-23 ring-opening polymerization, 32139-141 n-Silaallyltricarbonyliron complexes, synthesis and properties, 32137-139 19:230-231 Silafulvenes, synthesis, 39:76 Silaamidide salts, 39185-188 Silagermaoxacyclohexene, 39297 Silaaromatics, 3983-84, 150-151 Silaisonitrile, 39:161, 188-189 l-Sila-3-azacyclobutanes,39131 Silametallacyclopentanes, 19216-222 Silaazetidines, formation, 39128 reaction with alkynes, B216 Silaaziridine, 39132 Silanediimines, 39183-185 Silabenzene, 3976, 100, 102 Silanediyl, 39222 and isomers, calculations on, 2522 Silanes Silacarbocyclization, 43242-243 direct18C-'H coupling constants, 12:162- Silacyclobutanes, 32133, 3973-75, 91, 106 163,203-204 ring-expansion reactions, 43253 disproportionation, 19220-221 ring-opening polymerization, 19215-217 hydrogen-deuterium exchange, 19218 catalysis by platinum complexes, reaction with 19215-216 low valent metal complexes, 19217, Silacyclobutenes 247-248 silenes from, 3973-75 organocopper compounds, a285 Silacyclohexadienes, 15125-126 redistribution, 6:219 Silacyclohexene, 19216, 39:139 via rhodium silylene complex, 19:222 Silacyclopentadiene, 15124, 19228-229, telomerization with butadiene, 3984-85, 98 1T162-165 reduction with potassium, 15279 mechanism, 12164 Silacyclopentadiene complexes, aromatic, trisubstituted, radical reactions, U83, 85 39238 Silanethione, 39257 Silacyclopentadienide anions, 3822-25 Silanimines, 39194, 285 Silacyclopentenes, 13151-159, 32133 Silanitrile, 39189-190 Silanol 284

Silanol, 638, 9269, 39251 organometallic derivative anionic derivatives, 9272 structure, 31:280-284 Group I11 compounds, 9273 aluminum polycycle, 3k283 Silanone, 39123, 257 dimetallasilazane, 3k281-282 Silaorganometallic chemistry indium dimer, 3k282-283 coactivation reaction, 36269-271 magnesium cube, 3k283 complexes monomeric and cyclic molecule, cyclic, %272 3k280-281 disilaethene, 36275-276 secco norcubane-like polycycle, donor-stabilized, 36:272-274 3k284 silaethene, 36:274-275 synthesis, 31:276-280 silaimine, %275 from amide, 3k276 silatrimethylenemethane, 36276 condition, 3k278 silylene, 36232-268 from cyclic cis amine, 3k277 complexes, silylyne, 36272 metallacycle formation, 31:277-279 metallasilaallenes, 36276-277 from oxoamine, 3k277 prospects, 36277 synthetic use sila, 36:275-276 alkylating agent, silicon, and tin halide, Silaphosphahetereocyclobut-3ene,39212 3k285 Silaphosphimine, 2k269-270 base addition, 3k285 Silapropadienes, via photolysis of alkynyldis- polymetal ilanes, 1988-92 from alkyl metal silazane, Silaseleniranes, 39132 3k286-287 Silatetrazolines anion, 3k294 cycloreversion reactions, 24.232-233 bond distance, 3k290 preparation, 24:204-205 bond reactivity, 31:290-291 protolysis, 24235-236 dimagnesium with differing organic thennolysis, M232-233 ligand, 3k291 Silathiiranes, 39132 Grignard reagent, 3k293-294 1-Silatoluene, IR spectroscopy, 39100 lithium and aluminum, 3k286 Silatranes, in biology, 18291-294 lithium and indium, 3k286 activity, 18291, 293-294 property, 3k287 stimulation of protein synthesis, structure, 31:287-290 18293-294 two-coordinate sodium, 3k293 Silatriazacyclopentenes, 39133 X-ray diffraction study, 3k291-292 Silazane Silene, 7:39,3972-73,151-152,159,194 intramolecular bond fluctuation acyclic, synthesis, 3976 chelate Auner-type, reaction with quadricyclane, bond breaking and rotation, 3k295 39:120 enantiomeric form, 3k295-296 &1-SN2 borderline mechanism, 3&273 electron rich and deficient center, Brook, see Brook silenes 3k294 chemical shifts and coupling constants, ligand exchange 2514-15 conformer, 3k297 derived from photolysis of enantiomer equilibrium, 31:296-297 acyldi-or polysilanes, 2533-35 steric effect, 3k296 aryldisilianes, 2532 magnesium amide, 3k297-298 dimerization of, 2523-26 'H NMR spectrum, 3k297 empirical and structural formulae for, rapid-rocking, 3k298 252-5 solid state energy minimum, 31:295 experimental handling, 3993 Silicon

heats of formation, 2521 vibrational frequencies, 2520 history of, 251-2, 5-7 Woodward-Hoffman rules, 39104 ionization potentials, 2521 Silene-anthracene adduct, rearrangement re- IR spectra, 2510-15 action, 39148-149 kinetics Silene, elimination-addition reaction chemical reactions, 39112, 114 condensed phase, -269-271 dimerization, 39:108 anion-induced, 30:269 preparation, 3990-92 internal nucleophilic displacement, rates of reaction, 3914-15 M270-271 molecular rearrangement of, 2535-37 lithium silylamide, 30:269 NMR spectra, 2516 trisyl, 30270 n-bond strength, 2519 gas phase, 30266-269 photoelectron spectra, 2518 thermal, M268-269 physical properties, 3993-102 Silene-silylene rearrangements, 39138-1 39 bond length, 3994-95 Silene-solvent complexes, 3990 computations, 39:lOO-102 Silene-transition metal complexes, 39:85-89 geometric isomers, 3995 Silenolates, 3978-79, 119 spectroscopy, 3995-100 Silepin derivatives, from vinylsilanes and thermal stability, 39:95 Si=C compounds, 1978 preparation, 3972-84, 90-92, 140, Siletane, 3991 142-143 Silica, support for transition metal catalysts, reactions, 39:102-151 15194-1 96 bimolecular, 39133-138 Silica-supported triosmium clusters, as cata- with carbonyl groups, 39:122-128 lysts, 26:63-65 cycloadditions, 39:103-104, 111-1 13 Silicates, as skeletal components, dimerization, 39:104-111 18:275-276 end reactions, 39114, 117, 128-130 Silicon with imines, 39:128 alkyl derivatives of heavy alkali metals, kinetics, 3990-92, 108, 112, 114, 43280, 283-286,288-289,291 149-150 alkynyl complexes, 38101-102, 104, rearrangements, 39:138-149 116-117 reactivity of, 2521 applications of organosilanes, 43198 silaallene and isomers, 2522-23 arene bond formation, 43228-232 silaaromatics, 39:lSO-151 carbon bond formation, see Carbon-sili- silabenzene and isomers, 2522 con bond formation silicon-carbon double bond carbosilane synthesis, 35225-228 addition of s-bonded reagents to, as central atom in p complex, 26:288 2527-28 Direct Process Reaction, 3860, 67-69, length, 2517-18, 20-21 74-75 singlet triplet energy levels, 2519 dissociative pathway, substitution, stable n-bonded compound, 30266-267 30243-307 physical properties, -267 heterocarborane synthesis geometry, 30:130-137 1,2-eliminations, 2910 "Si NMR spectra, 30:135-136 photochemical, 259 structure, -132, 134-135 thermal, 257-9 synthesis, 30:130-135 theoretical prediction, 30265-266 multiple bonding, 39194 n bond energy, -265-266 organic derivatives, see Organosilicon n bond length, 30:266 compounds ultraviolet spectra, 2516-17 terphenyl derivatives, M32-33 Silicon 286

in triosmium clusters, W.68-69 silyloxycarbenium, 30:276 Silicon-arsenic multiple bonds, 39193-195 silyloxyphosphonium, 30276 arsasilenes, 39:220-227 silylphosphoniurn, 30:276-278 theory, 39193-195 structure, 30277-278 Siliconates, 20286 salt properties, 30282-283 Silicon-bridged [lJferrocenophanes, 32163 silylation catalysis, 30274-276 ring-opening polymerization, 32136-151 Silicon compounds Silicon, cage and cluster compounds, alkoxy derivatives, 631 321-14 isocyanides, 5182-183 hexasilaprismane, 321-4, 23-26, 36 via metal atom synthesis, 15106-107 octasilicubane, 37:l-4, 14-17, 36 metal derivatives, 6:45 tetrasilatetrahedrane, 321-4, 8, 34-36 methyl, in transmethylation, 20323 Silicon-carbon double bond nitrogen-containing, 641-42 addition of s-bonded reagents to, organometallic, synthesis, 392 2528-32 organoselenium derivatives, 581 addition of s-bonded reagents, to, organosulfur derivatives, 551-52, 59, 64, 2527-28 66-67, 69,71-72,74-76, 80 length determination, 2517-18,20-21 organotellurium derivatives, 5:81 Silicon-carbon double-bonded intermedi- a-bonding, 545-47 ates, 19:74-88 pseudohalides, 642-43 from benzenoid aromatics, 1975-82 radical anions of organo-derivatives, molecular orbital calculations, 19534 photolytic generation, 1959 15278-310 from a-alkenyldisilanes, 1984-88 sulfur derivatives, 642, 44 from alkynyldisilanes, 1988-92 Silicon compounds, structure and bonding from aryldisilanes, 1975 bond dissociation energies, 33129-132 from naphthyldisilanes, 19:82-84 divalent state stabilization, 33129, from pentaphenylmethyldisilane, 1974 131-132 vs. thermal generation, 1975, 84-85 M-H and M-M', 33130 reactions monosubstituted silanes, 33131 with alkynes, 1979-80 bond energies, 33135 with conjugated carbonyls, 1980-81 bonding considerations with dienes, 1978-79, 88 CH, compounds, comparisons to, dimerization, 1985 33135 with ketones, 1980,86-88 Jahn-Teller effect, second-order, with methyl Grignard reagent, 33135,138 1981-82 linearity vs. pyramidalization, 33135, with methyllithium, 19531-82 138 with olefins, 1976-77 parent hydrides, 33135-140 silepin formation, 1%78 bonding considerations, MR2 compounds with vinylsilanes, 1978 differenccs vs. CH, series, 33:140 Silicon cation, tetracoordinate geometry, 33137-138 nucleophile-assisted substitution, HOMO-LUMO interaction diagram, 30273-298 33139 mechanism, 30274-275 bonding considerations, MR3 compounds stereochemistry, 30:275 geometry, 33135-136 salt formation, 30:276-280 HOMO-LUMO interaction diagram, electrical conductance, 30277 33136 NMR spectroscopy, a278-280 divalent state stabilization energies, silylammonium, 30276, 278 33~131-135 287 Silicon

, comparison to, reactions with 33133 carbon-centered radical, 44:74, 77, heats of formation. dependence on, 79-81 33:134 nitrogen-centered radical, M81 monosubstituted silanes, 33131 oxygen-centered radical, M83, 85 n-bond energy, 33134-135 Silicon-nitrogen bond formation quantum mechanical studies, dehydrogenative-coupling reactions, 33132-133 43254-255 RR’M, preferred values for, 33131 double silylation of nitriles, 43256-257 doubly bonded hydrosilylation of nitrogen-containing sub- bond energies, 33:141, 143-145 strates, 43255-256 disilene, 33150-153, 155, 159 Silicon-oxygen bond formation divalent state stabilization energies, double silylation of carbonyl-containing 33141,143-145 compounds, 43251-252 isomeric energy differences, 33141, 143 hydrosilylation of carbonyl-containing silene, 33145-149 compounds, 43250-251 triply bonded silane alcoholysis, 43:248-250 dimethyldisilyne, 33164 Silicon-phosphorus multiple bonds, disilyne, Si2H2,33:161-163 39193-195 electronic structure vs. stability, phosphasilenes 33:163-164 metastable, 39999-200 SiCH2, 33161 transient, 39197-199 structural complexity, 33:161-162 theory, 39193-195 substituent effects, 33164-165 Silicon-silicon bond transition states, 33163 cleavage, 431-35,678 Silicon difluoride, reaction with aromatic in ferrocene derivatives, 6:74 compounds, 677 in polysilanes, 625 Silicones, 1314 energy, 429-30 early work, 97 formation by dehydrogenative coupling, Silicon, extended coordination 43243-245 reaction, nucleophile, 30296 homolytic scission, 1955 mechanism, 30296 length, &29-30 substitution pathway, 30294-296 photolytic chain contraction, 19:54-55 factor favoring, 30295 reactions, 435-38 hexacoordinate, 30296 Silicon, stereochemistry of nucleophilic dis- pentacoordinate, 30295-296 placement, 20265-312 Silicon, halosilane comparison with regioselective attack at Bronsted base catalysis, 30297-298 a-enones, 20283-285 Lewis base catalysis, 30297 alane reactions, 20283 nucleophile-induced inversion, organometallic reactions, 20283-284 30289-294 cryptand effect, 20282,293-294 activation parameter, 30291 and frontier orbital approximation, kinetics, 30289-291 20287-307 mechanism, 30289 alane reactions, 20295-297 NMR study, W291-293 alkoxide and thiolate displacement, pseudorotation mechanism, 30293-294 20291 racemization, W289 alkoxide coupling, 20298 transsilylation, 30:291 alkyl Grignard reactions, 2&294-295 Silicon hydrides alkyllithium reactions, 20293-294 kinetic isotope effects, M103-104 allyllithium reactions, 20.295-296 Silicon 288

and angle-strain at silicon, 20299-300 hydrogen, 1k276 fluoride vs. thiolate, 20992 by reductive elimination, 1k277 halogen leaving groups, 20290-291 solvolysis, 1k273-275 hybridization changes, 20304-305, 307 transmetallation, 11:278 leaving group electronegativity. 20288 dimensions, 1k281-282 major interactions, 20287-289 hydrogen-bridged, 1k290-291 nucelophile effect, 20288-290 insertion reactions, 1k278-279 phenoxide reagents, 20298-299 ligand exchange, 1k281 shapc of U*S,.~orbital, 20287-290, 293 substitution silicon-hydrogen substitution, 20:290 at metal, 11271-273 inversion and Si-X bond stretching, at silicon, 1k270-271 20272 Siliranimine, 39132 leaving group cffect, 20267-275, 290-293 Silirine derivatives, 13147 in acyclic organosilanes, 20270-271 dimeric nature, 13147 basicity, 20:269-270 Silole, 3822, 3985, 98 in bifunctional organosilanes, 20268- Siloxanes, 95 269, 271 from halopolysilanes, 630 case of displacement, 20268-269 structures, 640-41 halogens, 20:268, 290-291 synthesis. 6:39-40 polarizability, 20270 *‘Si NMR spectra, 23199 silicon-hydrogen displacement, 20267- and DEPT technique, 23:lYY-202 268,290 and INEPT technique, 23199-202 and stereochemistry, 20269-271 redistribution reactions, 19234-247 nucleophile effect, 20275-287,293-299 Siloxanes, in biology effect of metal counterion, 20276 cis-2,6-diphenylhexamethyl- electronic character, 20:278, 285 cyclotetrasiloxane, 18:289 hard and soft character, 20278-283, X-ray structure, 18292 287-290 estrogenic activity, 18288-289, 291 organolithium vs. Grignard reagents, as holders of active groups, 18291 20279-282 phenyl derivatives, 18288-291 in phenoxide coupling, 20:282-283 structure and activity, 18289-291 pentacoordination, 20272-275 ring conformation, 18290 pseudorotation and stereochemistry, Siloxetanes, 39123-125, 127, 146-147 20276-277 Siloxy-metal derivatives, 1k296-297 reactivity of bicyclic systems, 20306-307 Siloxymethylation, 43232-236 relative apicophilicity of bonded groups, Siloxysilene, 3822 20272-275 Silver NMR studies, 20273-275 alkyl halide adsorption on, 3&64 silacycloalkanes, 20299-307 reaction with alkyl halides, 3872 butanes, 20305-306 in triosmium compounds, 2675-76 pentanes, 20304-305 Silver complexes solvent effects, 20277-280 adducts of cluster compounds, 24106, of alcohols, 20280-281 124 Silicon transition metal bonds, 1k253-297 arene, 13122 addition at silicon, 1k279 X-ray structural studies, 1324-125 at transition metal, 1k280 bimetallic, 32253, 255-257 back-bonding, 11:282-283 borane, 2k65 cleavage, 1k273-279 as hydroformylation catalysts, 1755 with chloroalkanes, 11276 photochemistry of phosphinebutyl, 24325 halogens, 11:276 via metal atom synthesis, 15104 289 Silyl azides

ylide, 20153 kinetic isotope effects of insertion, Silver heteronuclear clusters 4317-18 with ligands other than two-electron do- lifetimes, 43:16, 26 nors attached to IB metals, reactivity towards silyene traps, 29334-335 4316-17 metal core arrangements, 2931.5, 318-320 solvent effects on insertion reactions, with more than three Ag(PR3) units, 4317 29300-301 spectroscopic analysis with no ligands attached to Group IB IR spectroscopy, 4311-12 metals, 29326-328 NMR, 43:13, 37 synthesis using anionic precursor, 29251 ultraviolet-visible absorption spectros- Silver(1) adducts, of carbonyl phosphine COPY, 4311-15 complexes synthesis iron, 2325 chemical, 4329,31, 33-34, 36-40 molybdenum, 23:14 irradiation of oligosilanes with Lewis rhodium, 2359-60 bases, 4319-22, 24-29 Silyene thermolysis in, 4331-34 comparison with carbenes, 431 thermodynamic calculations of complex reaction with Lewis bases, 431-2 formation and reactions with various Silyene complex, bridged nucleophiles alkyne reactions, 42284 carbon nucleophiles, 433-4 dimerization of mononuclear silylene chalcogen nucleophiles, 436-9 complexes, 42246-247 group 15 nucleophiles, 434-6 exchange reactions, 42286 halogen nucleophiles, 439-11 fluxional behavior, 42276-277, 279 Silyl anions, 381-2, 53 geometric isomerizations, 42279-284 alkylsilyl anions, 3811-16 ligands arylsilyl anions, 383-11 removal or addition, 42248 definition, 381 replacement, 42249-251 functionalized, 3816-25, 51 spectroscopy, 42272-273, 275 a-heteroatom-substituted, 3817 structure and bonding, 42265-266, 268- list of, 3850-52 269, 272 metal-free, 383 synthesis NMR data, 387-9,26-27, 48-49 disilanylene unit, rearrangement in polysilyl anions, 38:25-39 complex, 42246 preparation, 382-3 hydrosilane reactions synthetic applications, 38:39-45 carbonyl complexes, 42234-240 theoretical study, 3845-46 hydrido complexes, 42240-242 Silylation miscellaneous complexes, 42242-244 phosphorus acid, 30297 transition-metal complexes, silanol, 30297 42244-245 uncharged nucleophile-assisted substi- miscellaneous reactions, 42251-252 tution overview, 42224-225, 231, 234 amine catalysis, 30286 salt elimination reactions, 42245-246 base catalysis, 30297-298 Silyene-Lewis base complex configuration, W288-289 energy diagram of formation, 432-3 extended coordination, 30294-296 graphical representation, 432 kinetics, 30287-288 kinetic studies rate constant, 30288 flash photolysis, 4316 steric effect, 30286-287 formation rates, 4316 Silyl azides, 39161, 176, 178, 189 Silylcadmium 290

Silylcadmium, preparation, 383 salt adduct, 36265-267 Silylcarbene, 39143 Silylenes, addition reactions Silyl-cobalt compound, 382, 4-5 with alkenes, 1961-67 Silylcopper, preparation, 383 with carbonyl compounds, 1972-74 Silylcuprate, 383, 31, 40-43 with dienes, 1968-69 Silyldiazenes enolizable ketones, 1872-73 hydrolysis, 23152-155 with methylacrylate, 1973-74 as ligands, 23181 and rearrangement, 1968-69 properties, 23138-142 silacyclopropane formation, 1963-67 synthesis, 23133-137 Silylenes, base adducts thermolysis, 23144-149 bond distance, 36248 Silyldiazides, 39:290 coordination geometry, 36:242 Silyldiazoalkanes electronic structure, 36:247-248 decomposition, 3983 high-valent transition metal complexes, photolysis, 3974-76, 146 36248 silaaromatics from, 39:83-84, 150-151 NMR data, 36:245-247 Silylene complexes SCHAKAL plot, -244 base adducts, 36242-248 spectroscopic parameters, 36245-247 base-free, 36.267-268 structural aspects, 36242-244 base stabilization, 36251-265 structural parameters, W243 cyclic, M272 Silylenes, base stabilization, 36:251-265 donor-stabilized, 36:272-274 coalescence temperatures, 36:253 high-valent transition metals, 36:248-25 1 flip-flop coordination, 36259-261 metal, 19250-251, 39:269 fluxionality, 36.252-254 in disilane redistribution, 19227 intramolecular donor reactions, trapping with alkynes, 19227-228 36261-265 salt adduct, 36:265-267 intramolecular interaction, 36:254 Si-Si bond formation, 36237-242 ORTEP view, 36:255 synthesis, 36:242 phosphino substitution, 36258-259 p-Silylene complexes, 20231-237 silanediyl complexes, 36:255-256 Silylene (RZSi) complexes, 1k291-293 silanediyl coordination, 36256-258 Silylenes, k91, 3984-85, 240 Silylenes, dehydrogenative coupling reac- disilenes from, 39237-238, 248, 250-253 tions hydrosilation process, 36:231 early transition metals, 36240-242 insertion reactions, 19:60-61 late transition metals, 36:237-240 intermediacy in complex-catalyzed silane mechanisms, W240-241 disproportionation, 19222 silanes, 36232 as intermediate in Direct Process Reac- Silylene-silene rearrangement, 39138-139 tion, 3867-68 Silylene synthesis methylchlorosilane synthesis by direct base abstraction, 36:234 methods, 36231 dimeric cleavage, 36:235-236 photochemical generation, 1952-59 insertion, 36233-234 properties, 39:102 metal coordination, X235 reactions salt elimination, 36:232-233 dimerization, 39236 silane elimination, 36:237 with trityl azide, 39166 substituent displacement, -234 reactivity, 36248-251 trapping, X235 metal silicon bond retention, Silylenium ion W249-251 reaction intermediate at silicon center M-Si bond cleavage, X249 p-elimination, 30:263-264 291 Silylhydrazine synthesis

hydride transfer to carbocation, Silyl ethers, charge transfer complexes 30255-258 absorption peaks, 34:177 electrophilic attack, 30.255 formation, H.176-177 four-center transition state mecha- formation constants, 34178 nism, 30255 mechanism, 34:177 single electron transfer mechanism, tetracyanoethylene(TCNE), M174-176 30258 Silylformylation, 43236-241 SN2mechanism, 30256-258 Silylhydrazines, anionic rearrangement, Lewis acid, 3tk264-265 163-4 1,2 migration, &-functional silane, Silylhydrazine synthesis 30258-260 hisf hydrazin0)silanes chemical trapping, 30260 crystal structure, &27 previous mechanism, W258-259 synthesis, &24-26 nucleophilic substitution, trisyl species, bis(sily1)hydrazines 30260-263 asymmetrical compounds, &9-10 anchimeric assistance, 30262-264 isomerization, 4&6 bridged mechanism, M261-262 lithiated compounds, crystal structures reactivity, W261 dilithiated compounds, 4M4-17 racemization, 30263 monolithiated compounds, &lo-12, solution, search, 30250-254 14 carbenium ion analog, 30251 sialtropy, 40:7 controversy, 30254 symmetrical compounds, 4&6-9 hydride transfer, 30251-252 cyclic compounds NMR spectroscopy, 30:252-253 bicyclic systems, &38-41 silyl halide, 30253-254 classification, &27-28 silyl perchlorate, 3lk252-253 Silylenium ion intermediate crystal structures, &29-30, 35-36, ab inifio calculation, 30945-246 39-41 carbenium comparison, 30:245-246 diazasilacyclopropane, 40:28-29 gas phase four-membered ring systems, 40:29-30 generation, 30246-250 seven-membered ring systems, chemical nuclear decomposition, 40~37-38 30247 six-membered ring systems, 40:33-37 ICR mass spectroscopy, W246-247 hydrazine treatment with halosilane, &2, kinetics, 30247 9, 17, 21-22 photoelectron-photoion coincidence, lithiated hydrazine treatment with halosi- 30.247 lane, 40.2-3 tandem mass spectroscopy, mono(sily1)hydrazines 30247-248 lithium derivatives, &4-6 physical properties, M250 properties, &3-4 reaction, 30249-250 nitrogen oxidation state, 40:l addition complex, 30249 tetrakis(sily1)hydrazines intramolecular rearrangement, crystal structure, &22-24 30249 synthesis, 40.20-22 mechanism, 30249-250 tris(hydrazino)silanes, &26-27 solution comparison, 30:250 tris(sily1)hydrazines nomenclature, 30244 crystal structure, &19-20 theoretical study, 30244-246 isomerism, &18-19 Silylenoids, 38:47 synthesis, &17-19 Silylenol ether, 1972-73, 39262 types, 4tk18i Silylhydroxylamine rearrangements 292

Silylhydroxylamine rearrangements, 16:14- electronic structure, 23139, 142 18, 55-58 properties, 23138-142 Silylidenearsanes, see Arsasilenes protolysis, 23155 Silylidenephosphanes, see Phosphasilenes reaction with diorganylboron halides, Silylidenesilanes, 39194 23161-162 Silyllithium, 3846-47, 3988 thermolysis, 23149-152 allyl-bearing, 385 of methyl derivatives, 23149-151 optically active, 386 Silylpentazene, 24246-247 polysilane redistribution with, 38:35 Silylphosphanes, 39208 preparation, 38:2, 4-5 Silylphosphine imines, 9308-314 reaction with chlorosilane, 3810-11 bis(phosphorany1idene)ammonium salts, tin-substituted, 3831 9314 Silyllithium compounds coordination compounds, 9310 cleavage of cyclosilanes, kll5, 117 hydrogen halide adducts, 9310 cleaving agent. k106 metal alkyls, 9311-313 from Compound C, 1:102 phosphonium salts, 9313 preparation, k106 Silylpotassium, 382, 5, 17 Silyllithium reagents, 3979 Silyl radical species, k137 Silylmagnesium, preparation, 38:2,4-5 Silylsodium, 38:2, 46 Silylmagnesium reagent, 3836-37 Silylstannanes, 3843 Silylmanganese reagent, 3836-37 Silylsulfides, charge transfer complexes Silylmercury, preparation, 383 absorption data, N176 Silylmercury compounds, 386, 12 ionization potentials, 34175 Silylmetal complexes, in redistribution reac- perturbation of molecular orbital tions, 19247-251 method, 34:175 mechanisms, 19:247-251 Sandorfy C method, a176 silylenoid intermediates, 19249-251 spectral parameters, 34174 Silylmetal compounds, 743 te tracy anoethylene , 34174- 176 Silylmetallic reagent, 3974, 78 Silyltetrazenes Silylmethyl group, transition metal deriva- of arsenic, 24241, 243 tives, 1k310-323 of beryllium, 24240-241 polymerization of a-olefins, 11:322 of boron, M240-242 reactions, 1k321 catalytic hydrogenation, 24234 synthesis, 1k318-321 halogenation, 24233 Silylmethyl radicals, 9278 hydrazones, 24242-243 Silylonium ion complex isomerization, 24215-219 dynamic behavior, 30284-286 lithiated derivatives, 24239-245 dissociation-recombination pathway, 1,3-migrations, 24:217, 219 30285-286 nitrogen-chain extension, 24.245 ligand exchange, 30284-285 of phosphorus, 24241,243-244 phosphorus acid generation, 30:285 photodecomposition, 24:216 silyl exchange, 30285 physical properties, 24207-21 1 extended coordination, comparison, ultraviolet spectrum, M215 30:294-296 protolysis, 24:235-237 nucleophile-catalyzed inversion, 30294 p-quinone reactions, 24233-234 thermodynamics, 30280-284 radical cation formation, 24234 enthalpy, entropy, 30280 reduction, 24:234-235 equilibrium constant, 30284 structures, 24212-213 NMR equilibrium study, 30281 substitution reactions, 24237 Silylorganyldiazenes of sulfur, 24:241, 244 Sodium

synthesis, 24202-208, 210 zeolites, 22236-237 thermolysis, 24:220-231 Sodium bis(trimethylsilyl)amide, reaction Silyl-transition metal complexes, 11:253-323 with metal carbonyl derivatives, anionic derivatives, 1k295-296 1838-42 IR and Raman studies, 11:285 deprotonation of coordinated ligands, mass spectrometry, 11:287 1841-42 NMR studies, 1k286 acetonitrile, 1841 synthesis, 1k263-270 cycloheptatriene, 18:41-42 by amine elimination, 11:267 synthesis of cyanide complexes, 1838-41 by hydrogen elimination, 1k265-266 Sodium 2-bromoethylsulfonate, 38:164 by hydrogen halide elimination, 1k267 Sodium graphite intercalation compound, metathetical reactions, 1k263-264 2896 oxidative addition or elimination, Sodium-lead alloy, in preparation of tetra- 1k268-269 ethyllead, 38:68-69 from silylmercurials, 1k265 Sodium naphthalide, electron-transfer reac- Silyltriazenes tions, 15275 cis-trans isomerizations, 24194-195 Sodium, organometallic compounds, X-ray hindered rotation, 24197 structural analysis, 22169-277 and d,-p, bonding, H198 aggregation, 22180 1$migrations, 24:195- 197 alkyls, 27:191-193 physical properties, 24:190-193 alkynyls, 22194-196 reaction with metal carbonyl halides, aryls and alkenyls, 22192-194 M189, 192 benzyl compounds, 22196-199 synthesis, 24:180, 182-188 bond lengths, 22186-188 thermolysis, W.198-202 bridging, 22178 Silyl vinyl ethers, 39256 without carbon-metal interactions, Silylzinc, preparation, 383 22245-247, 251-252, 254-256, 258 [SiMe3(C6H4-4-CH=C(CN)2],nonlinear op- charge delocalization, 22173 tics, 42344 coordination, 27:176 [SiMe3(C6H4-4-NMe2)],nonlinear optics, cyclopentadienyl derivatives, 22201-202 42338, 343 graphite intercalates, 27:208 [c-SihMel,)-SiMeH2lz, synthesis, 42:388 ionicity, 27:176 Simmons-Smith cyclopropanation, olefins mixed metal compounds, 22211-221, with zinc-diiodornethane, ultrasound ap- 223-227,246-247,251-252 plication to, 25108-109 polyphenyl radical anions and dianions, Simmons-Smith reaction, l2:85-93 22205-206 Singlet triplet energy, in silenes, 2519 Sodium salts, anionic hydride complexes Slater orbitals, 153 spectroscopic properties, 224-8, 24-27 1-Sodio-l-t-butyl-2,3,4,5-tetraphenylsila- structural properties, 2218 cyclopentadiene, 3823 Sodium, synthesis and structures of organo- Sodium metallic compounds colloidal, ultrasound analysis, 25107 alkene derivatives, overview, 43309, 311, cyclopentadienyl complexes, 26:224-225 326 metal-carbon bond lengths, 43342-343 alkylalkoxide intermediates, 43291-292 physical properties, 22174 alkyl group exchange, 43270 safety in handling organometallic com- alkyne derivatives, 43326 pounds, a269 ally1 derivatives, 43311-313, 315-319 solvation energy, 22182 arene derivatives, 43:326-332, 334-341 structure determination of organometallic azaallyl derivatives, 43319-320, 323-324 compounds, 43268, 271-272, 342 azulene derivatives, 43:307 Sodium 294

benzyl and related derivatives, Sonochemistry 43271-275 apparatuses, comparison with photochem- cumyl derivatives, 43:275, 277 ical apparatuses, 2587 cyclopentadienyl derivatives aqueous, chemical effects of ultrasound, substituted derivatives, 43299-301, 304 2592-93 unsubstituted derivatives, 43294-297, effect of 299 acoustic frequency, 2587-88 fluorenyl derivatives, 43305-306 acoustic intensity, 2588 fullerides, 43341-342 ambient gas, 2588, 90 indenyl derivatives, 43304 bulk solution temperature, 2588-89 methyl derivatives, 43271 solvent choice, 2588, 90-91 organolithium reagents, a269 static pressure, 2589 organomercury reagents, 43269-270 nonaqueous, chemical effects of ultra- pentalene derivatives, 43:308 sound, 2594-95 phenyl derivatives, 43292-294 of non-carbonyl organometallics, silicon-substituted alkyl derivatives, 25100-101 43~280,283-286, 288-289, 291 organometallic triphenylmethyl derivatives, 43277, 280 application to heterogeneous catalysis, Sodium terphenyl, radical anion and dia- 25:110-111 nion, 22205 initiation of homogeneous catalysis, Sodium-tin alloy, 3869 25101-103 Solid-state NMR spectroscopy stoichiometric reactions in heteroge- room temperature, 28451-455 neous systems, 25103-110 variable temperature, 28:455 stoichiometric reactions in homoge- Solid-state structure, phosphinocarbenes, neous systems, 2595-101 a185-186 reactor design and configuration, Solution studies 2584-87 interaction in tin compounds, 982 Soybean oil methyl ester, homogeneous hy- structures, 985 drogenation, 13:329-330 Solvation energies, in alkali organics, Speciation, and biomethylation mecha- 27182-184 nisms, 20340-343 Solvatochromism, 3360-63 Spectral studies, of titanium trihalide com- Solvent coordination effects, in organomet- plexes, 9147 allic compounds, 230 Spectroscopic energies, 928 Solvents, interaction with GIC, 2897-98 Spectroscopic properties Solvent-silene complexes, 3990 anionic transition metal hydrides, 274-8, Solvochromism, measurement of organomet 20-27 allic second-order nonlinear optical organoplatinum(1V) complexes, properties, 42303 22131-143 Solvolysis transition metal carbynes, 2255-56 acyl, reactions, computer representation, tungsten alkoxides, 22314 26194 Spectroscopic studies norbornadiene complexes, 10364 infrared, fluorocarbon metal compounds, pseudohalides, organometallic, 5193 k212-216 silicon transition metal bond cleavage, NMR, fluorocarbon metal compounds, 11~273-275 k206-212 steric effects in, 1k8 Spectroscopy, see also specific types of transition metal alkyls, 7~179 alkynyl-metal complexes, 3883-89, Sommer’s rule, leaving group basicity, 120-138 202269-270 diheteroferrocenes, 39342-343 Stability

disilenes, stable, 39240-247 benzohydroximato(2-) bidentate li- germanium doubly bonded compounds, gand, synthesis, 44255 39283-285 ethane-l,2-diolato(2-) bidentate ligand germenes, 44121 NMR studies, 44240 manganesepentacarbonyl alkyls, synthesis, 44239 32177-178 X-ray diffraction studies, 44239 phosphasilenes, 39204-206 ethene-1,2-diolato(2-) bidentate ligand polystannanes, 38199-203,210-214,216- ab initio studies, 44237-238 217,227-228,238 NMR studies, 44238-239 rheniumpentacarbonyl alkyls, 32179-181 synthesis, 44236 silenes, 3995-100 X-ray diffraction analysis, tin double bonded compounds, 44 23 6 - 2 3 7 39306-309 a-hydroxycarboxylic acids Speier's catalyst, for hydrosilylation, 11:298 ligands, 44240-241 Spin-lattice relaxation times, in I3C NMR NMR studies, 44247, 249-251 spectra, a151 synthesis, 44242-245 of carbon, Q137-138 X-ray diffraction studies, 44245-246 reduction by paramagnetic compounds, naphthalene-2,3-diolato(2-) bidentate 12137-138 ligand Spin-saturation transfer techniques, NMR ab initio studies, 44232-233 spectroscopy, 16221-222 chemical properties, 44235 in 'H studies, 16222 geometry optimization, 44232-233 Spin-spin coupling constants, theoretical cal- synthesis, 44230 culation, 33 X-ray diffraction analysis, Spin traps, 14347 44230-233 for pentacyanocobalt(I1) salts, 15313 naphthalene-2,3-diolato(2-) bidentate in SH2reactions at Pt(II), 14376-378 ligand, NMR studies, 44233-234 Spiroarsines salicylato(2-) bidentate ligand reactions, 4176-177, 179, 181 NMR studies, 44254 synthesis, 4152 synthesis, 44252 Spiro boron atom, 2274-275 X-ray diffraction studies, 44252-254 Spirocyclic sulfur systems, 57, 10, 12 with Si02N2Cskeleton Spirocyclic zwitterionic h5Si-silicates NMR studies, 44258-259 with Si0,C skeleton synthesis, 44257 acetohydroximato(2-) bidentate ligand, X-ray diffraction analysis, 44257 NMR studies, 44255-256 with Si02S2Cskeleton acetohydroximato(2-) bidentate ligand, NMR studies, 44261 synthesis, 44255 synthesis, 44260 benzene-l,2-diolato(2-) bidentate X-ray diffraction analysis, 44260-261 ligand with Si05 skeleton ab initio studies, 44232-233 NMR studies, 44263-264 chemical properties, 44235 synthesis, 443262 geometry optimization, 44232-233 X-ray diffraction studies, 44262-263 NMR studies, 44233-234 synthesis, 44228 synthesis, 44229-230 Spiro[4.4]nona-1,3-diene,reaction with tri- X-ray diffraction analysis, carbonyl-h6-1,3,5- 44230-233 cycloheptatrienechromium, 26326 benzohydroximato(2-) bidentate li- Stability, of transition metal alkyls(aryls), gand, NMR studies, 44255-256 2175-177 Stability constants 296

Stability constants, of methyltin halide com- solution chemistry, 33217-218 plexes, 1481-82 triptych compounds, 33217-219 Stability factors, transition metal com- Stannenes plexes, 2:169-172 molecular structure, 39:304 Stannaalkanes, 33174 reactions, 39315-316 Stannacarborane bipyridyl adduct, 26244 spectroscopy, 39306 Stannacubane, 3220 synthesis, 39310-311 Stannacycloalkanes Stannocene, see also Dicyclopentadienyltin CISII[(CH~)~],,33177 Mossbauer spectroscopy of substituent ef- 1,3-distannacyclobutane, 33174 fects, 40:160-161 PhSn[ (CH2)&, 33:175 Stannoles, reactions, 39327 synthesis, 33173-175 Stannols, 9269 1,2,4,5-tetrastannacyclohexanes,33176 lithium derivatives, 9272 Stannacyclopropene, 38232 Stannyldiazenes, 23133, 137-138 Stannaethene, 39317 p-Stannylene complexes, 20231-237 [l]Stannaferrocenophanes,32163 Stannylenes, 38:232 Stannagermene 1,2-distannacyclobut-3-enes,33178-179 physical properties, a142 formation, 39309 reactivity, 44.142-143 molecular structure, 39304 synthesis, M142 reactions, 39308 Stannaketenimine l-stannacyclohexa-2,5-dienes,33179-180 molecular structure, 39304-306 1-stannacyclopentadienes,33179 reactions, 39313 1-stannacyclopropene, 33178 spectroscopy, 39306-308 Stannylphosphine, synthesis, 39319 synthesis, 39312 Stannyltetrazenes Stannane, see Organotin hydrides isomerization, 24217-218 Stannaneselones photodecomposition, W216 preparation, 39:309-310 physical properties, M207-209, 215 reactions, 39313-314,319 protolysis, 24237 Stannanethiones reaction with oxygen, 24233-234 preparation, 39309-310 substitution reactions, 24237-239 reactions, 39313-314, 316, 318-319 synthesis, 24.206, 208 Stannanimines thcrmolysis, 24220,224-228, 230-231 molecular structure, 39306 Stannyltriazenes reactions, 39314-315,317 319 physical properties, 24190-191 spectroscopy, 39308 radical reactions, M193-194 synthesis, 39312,316 reactions with metal carbonyl halides, Slannauone, reactions, 39:315 W189, 192 Stannaoxaphosphorinenes, 39315 synthesis, 24180,182, 187-188 Stannaphosphenes Static pressure, effect on sonochemistry, preparation, 39310-31 1 2588-89 reactions, 39314-315, 318-319 Stereochemical nonrigidity spectroscopy, 39308 mononuclear transition metal complexes, Stannaphosphimines, 2k271 16319 Stannaselenaphosphirane, 39318 organometallic compounds, 16319 1-Stanna-4-sila-2,5-hexadienes, 33182 Stereochemistry Stannatctrazole, 39317 addition of BZC14to multiple bonds, Stannatranes 10:254 diptych compounds, 33217-219 arylsilyl reactions, 3810-11 reaction chemistry, 33218-219 of carbonylation reactions, 1k112 Stretching vibrations

decarbonylation, 1k112 solid angles, 36115, 117-130 electrophilic substitutions, 1025 advantages, 36:123 metal enolates, 1017 atom overlap problem, 36126-128 of olefin metathesis, 1E468-482 Bondi data set, 36126-127 organocobalt(II1) complexes, 1k343-349 cluster size calculation, 36124-125 oxidative addition reactions, 259 definition, 36121-123 phosphine complexes, determination by GEOME calculation, 36124 NMR, 260 ligand profiles, 36119-121 reactions involving optically active organ- MM2, force field, 36130 osilicon compounds, 7:123, 125, 128 molecular mechanics, 36117-118, 129 u,u-and u,a-conjugation, 1023 M-P bond rotation, 36119 Stereoelectronic control, of multistep reac- SYBYL force field, 36129-130 tions, 883 Taft-Dubois steric parameter, 36128 Steric effects, in organometallic chemistry, uses, 36122-126 see Organometallic chemistry, steric ef- sulfides, 36:116 fects Taft steric parameter, EfS,36134-136 Steric size quantification Steroids, silylation, 18:283-285 alkyl groups, 36110-114 ring attachment, 18284 amines, 36108-109 ring substitution and stereochemistry, aryl groups, 36110-114 18284-285 Charton’s regression analysis, 36136 and sex hormonal activity, 18:284-285 cluster cone angles, 36104, 116 Stevens rearrangement, 163, 162, 168 cone angles, 3697-117 Stibabenzene, 39325 bite angle, 36:103 Stibine imines, 9285 cone measuring device, 36102 Stibole, 39327, 333 definition, 3698 Stille coupling reaction, 35261 kinetic data, 36:101-102 Stokes lines, k242 measurements, 36:97-101 Strained cyclic alkyne-transition metal organopmetallic clusters, 36104-105 complex semivertex angle calculation, 36:102 notation, 42148 Tolman angle, 3697-101 stability, 42148 Tolman concept, 3697-104 synthesis and reactivity value modification, S103 eight-membered rings, 42197 ligand repulsive energy, ER,36130-133 five-membered rings, 42187-189 absolute static threshhold, 36132 [2.2]paracyclophane-l-yne,42197-1 99 atom-atom interaction model, 36133 seven membered rings, 42192-197 Buckingham potential, 36132 six-membered rings, 42189-191 linear free energy approach, Strained cyclic cumulene-transition metal 36131-132 complex ligands, 36117 notation, 42148 P(OR),, 36:108 stability, 42148 P(OR)A*, 36108 synthesis and reactivity P(OR)*A, 36:108 seven-membered ring allenes and PR?, 36105-107 higher cumulenes, 42202, 204- macrocyclic chemistry, 36134 216 molecular mechanics, 36:133-134 six-membered ring allenes and higher molecular volumes, 36145-152 cumulenes, 42201-202 applications, 36149-152 three to five-membered ring allenes charge distribution, 36148-149 and higher cumulenes, 42199-201 NMR spectroscopy, 36136-137 Stretching vibrations, k243, 248-251 Strontium 298

Strontium metal oxide film precursors, diacetamide compounds 40:317-319 physical properties, 40:296-297 monodentate donors, &320 synthesis, 40:291-292 polydentate donors, 40:320-324 graphite intercalation compounds, thiocarboxylates, 4Q:326-327 28:96-97 Strontium P-diketonates P-ketoiminates crystal structures, 40:276-278, 280, 282 physical properties, 40:265-271 mass spectrometry, 40:282-283 types, &272 physical properties, 40:265-271, 275, 281 monocyclopentadienyl compounds polydentate compounds physical properties, 40:297-298 crystal structures, 40:286, 289 synthesis, &292-293 mass spectrometry, 40:289-290 phosphides physical properties, 40:284-285 crystal structures, 40:230-231, 234-236 synthesis, 40:283-284 physical properties, 40:226-227, 230, synthesis, 40:273-275 232,234 types, 40.272 synthesis, 40:224-225,228-230 volatility, 40281, 283 polydentate ligands Strontium, metallocenes crystal structures, 40:302, 304-305, 307, crystal structures, 40:243-244, 246-249 309 gas-phase electron diffraction, 40:246 physical properties, 40:299-301 Lewis base removal, 40:237-238 synthesis of compounds, 40.298-299 mass spectrometry, 40:246 poly(pyrazoly1)borates physical properties, 40:239-243 stability, 40:236-237 physical properties, 40:250-251 synthesis, 40:237-239 structures, 40:250 Strontium sulfonates synthesis, 40:249-250 physical properties, 4k295-296 selenolates synthesis, a291 physical properties, 40:293-295 thiocarboxylates synthesis, 40.290-291 physical properties, 40.295-296 Strontium alkoxides synthesis, 40:291 crystal structures. 40255, 261-263, 265 Structural data, nitrogen-bridged iron car- NMR, a263 bonyls, 10120 physical properties, 40:255-259 Structural parameters of organometallic cya- synthesis, 40:253-255 nides, 5182 Strontium amides Structural studies crystal structures, 40:230-231, 234-236 acetytriphenylgermane, 7:117 physical properties, 40.226-227, 230, 232, of bridged electron-deficient main group 234 compounds, 15235-268 synthesis, 40:224-225, 228-230 beryllium, 15251-254 Strontium carboxylates magnesium, 15255-256 physical properties, 40:295-296 organolithium derivatives, 15255-262 synthesis, 40.291 carbon-metal bonds, 2174 Strontium. chemical vapor deposition iridium oxygen complexes, 264 alkoxides, 40:250,253, 263-265, 315 isocyanide complexes, 1k23 carboxylates, 40:324-325 metallasiloxanes, 9:267 cyclopentadienyl compounds, 40:311 metal nitrosyl complexes, 2213-216 P-diketonates metal-silyl complexes, 1k261-262, fluorinated compounds, 40:315-316 280-281 Lewis base adducts, 40:319-320 Co( CO)4(SiC13),11:283 299 Structure

FeH(SiCI&(CO) (aC5H5),11:284 acetylene-metal carbonyl complexes, RhHCI(SiCl,)(PPh,),, 11:284 5114-125 organocobalt(II1) complexes, 11:344 COq(C0)1z(EtzG), 5118 organophosphine imines, 9290 Co*(CO)g(HCZH), 5125 phosphine methylenes, 9:295-297 COZ(CO)~(HC~H)(HC~BU)~,5109 transition metal alkyls(aryls), 2174 Coz(CO)&'h,C2), 5116 Structural types, of triosmium clusters, Fe2(C0)6(HCZH)3(two isomers), 26:6-39 5122-123 Structure Fe2(C0)6(PhzC2),5121 alkali-graphite intercalates, 22207 Fe3(CO)R(PhZCZ)2(black isomer), 5120 alkali metal carbanions with no carbon- Fe2(CO)6(PhCzH)3,5123 metal interactions, 22239-242 Fe3(CO)R(Ph2C2)2(violet isomer), anionic transition metal hydrides, 229-20 5117 benzylic alkali metal complexes, HzFez(C0)8(MezC2),5121 27:197-200 perfluorocyclohex-1-yn-3-enedicobalt cyclooctatetraenepotassium compounds, hexacarbonyl, 5117 22205 ally1 complexes, 5105-112 cyclopentadienyl alkali metal complexes, a-ally1 palladium acetate, 5106 22201-203 n-ally1 palladium chloride, 5106 ethylsodium, 22193 bis(methallyl)nickel), 5106 methylpotassium, 22192 COZ(CO),( HC~BU)Z(CzHz), 5109 methylsodium, 22191 cyclooctadienyl palladium acetylaceto- mixed alkali metal compounds, 22208- nate, 5108 216, 218-235 dodeca-2,6,10-triene-l,l2-dienylruthe- molybdenum and tungsten alkoxides nium chloride, 5108 carbonyl complexes, 27:35Y-360 ethoxytetraphenylcyclobutenylpalla- dinuclear alkyl and aryl complexes, dium chloride, 5107 22347-348 eno-ethyltetramethylcyclobutenyl-a- dinuclear alkyne complexes, cyclopentadienylnickel, 5107 22338-339 Pd( C3HqMe)P(CbH5)$1, 5109-1 10 metallacyclobutadiene complexes, arene complexes, 598-100 22333-334 (ChHGPdAlzC1,)2, 599 mononuclear alkylidene complexes, conjugated diolefin complexes, 5100-105 22315-316 a-cyclopentadienyl-hexakis (trifluoro- mononuclear alkylidyne complexes, methy1)benzene-rhodium, 5100 22323-325 cyclopentadienone ligand, 5102 polynuclear alkylidyne complexes, a-cyclopentadienyl complexes, 594-98 27~353-354 ferrocene, 594 monosodium acetylide, 22195 nickelocene, 5119 organoplatinum(1V) compounds, 22121, nickelocene-dimethyl acetylenedicar- 138-141,144, 157 boxylate adduct, 5119 phenylsodium pentamethyldiethylene-tria- (T-C~H~)~MOH~,596 mine, 22193 ruthenocene, 594 potassium biphenyl radical anion, 22206 cyclopropane complexes, 5112-114 sodium terphenyl radical dianion, 27205 (C1HG)PtClzpyz, 5113 transition metal carbynes, 2753-55 duroquinone-cyclooctadiene-nickel, 5124 trimethylenemethane metal complexes, fluorocarbon complexes, 5125-128 27:289-294 (CF~)~C~R~(T-C~H~),5100 Structure, organometallic complexes, perfluorocyclohex-1-yn-3-enedicobalt 393-135 hexacarhonyl, 5117 Structure 300

lactone-cobalt carbonyl complex, 5: 125 Sugars, as part of chirdl phosphine ligands, metal carbonyl derivatives, 5128-131 17550-351 [FIFel(CO),,]~, 5128 and asymmetric hydrogenation, HMn3(CO)III(BHI)7.5129 12350-351 (s-B,C7HI i)Fe(n-CsHs), 5129 Sulfene complexes, reaction with dn alkyli- metallo-ring systems, 5:120-124 dene complexes of Ru, Os, and Ir, Fe>(CO)h(C2HL)jr5123 25166 Fez(CO)JPh,C,), 5121 y-Sulfido dialanes, 3944 Fc3(CO),(Ph2C2)(black isomer), 5120 0-Sulfinates, 12:33 Fe2(CO)6(PhC2H3),5: I23 intermediates in S-sultinate formation, H2Fe2(CO)#(Me2C2),5121 Q38-39, 50, 55 osmacyclopentadiene complex, 51 22 manganese and rhenium, 1262 trimethylgermanium cyanide. $184 molybdenum, 1260 trimethyltin cyanide, 5185 titanium and zirconium, 1259 trimethyltin fluoride, 5147 0,O’-Sulfinates, U:33 trimethyltin formate, 5149 of titanium, l259 ylid-platinum complex, 5113 S-Sulfinatcs, 1233, 47, 52 Styrene chromium, molybdenum, and tungsten. hydroformylation, 1216 Uh0-61 reactions cobalt and rhodium, 1266-68 with 1,2-digermacyclobutadiene,44136 desulfination, =SO-52, 57, 64 with digermenes, 44.138 gold, U70 Substituenl effects iron, 1261, 63-65 on Co-C bond cleavage, 1k412 manganese and rhenium, 1262-63 in nietallocene chemistry, 1079-111 nickel, palladium, and platinum, U:68-70 ligand exchange, 1091 from norcarane complex, a58 metal-ring bond, 1091 ruthenium, 1255 Substituted v4-dicnc metal carbonyls structure, 1234 dynamic behavior, m.303-310 Sultines ligand exchange, 26310-311 coordination modes. 36172 molecular structures, 26302-303 rnctal-carbonyl mediated reduction, stereochemistry, 26300-302 36174 synthesis, 26300 a-metallasultines, 36177-179 Substituted ring systems, synthesis, 867-74 oxidation addition, 36175 Substitution platinum complexes, 36175 electrophilic, see Electrophilic substitu- rcactivity. 36172-178 tion reactions rhodium complexes, 36176 in metal s-cnmplexes spectroscopic studies, 36173, 176, 178 associative mechanism of, 10349, 370 stepwise assembly, 36173 of ligands, 10347-409 structural studies, 36:178 at M-X bond by Pt(1) and Pd(1) com- a-subslituent participation, 36172 plcxes, 28282-283 synthesis, 36172-178 of nucleophile-carbonyl adducts, vinyl sulfine synthesis, 36:174 281 72-175 N-Sulfinylamines, see Iminooxosulfuranes Substitutioual compounds, 28249 Sulfonate estcrs, alkyl, 28101-102 Substitution reactions Sulfonato-complexes cobalt nitrosyl carbonyls, 2235 rhenium, U72 organocoppcr compounds, 12:259-260 by sulfur trioxide insertion into metal-al- in transition mctal carbynes, 27:95 kyl bonds, a72 30 1 Sulfur dioxide

Sulfoxide ligands, in asymmetric hydrogena- 0sand Ru carbyne complexes, 25191 tion, 12360 pentacyanocobaltate, 11:430 Sulfur rhodium ally1 complex, 16245 bridging by ketenes, 2810-11 reduction to hydrosulfide ion, 1816-17 Ge-S bond insertion, 44:126 Sulfur dioxide analogs B complexes, 26285-286 cumulenes, physical data, 36165 reaction with general coordination, 36:162-164 phosphasilenes, 39211 frontier orbitals, 36:164 tetracarbonyls, 29141- 142 group frequencies, 36:166 terphenyl derivatives, 4452-55 modes, 36162 Sulfur complexes orbital interactions, 36:164 cobalt, 3:239-240 relative energies, 36:165 iron, 3225-228,232-233,235 spectroscopic data, 36:164-166 manganese, 3215, 217, 222 theoretical considerations, 36162-164 mass spectra, 6:294, 302-303 insertion mechanism, 36:160 molybdenum, 3206,211,213 thiazate ligands, 36.217-221 rhenium, 3224 coordination chemistry, 36:221 rhodium, 3244 cothermolysis, 36220 tungsten, 3211 mechanisms, 36218 Sulfur diimides metals, 36217 cluster, 3621 1 platinum complexes, 36:219 coordination complexes, 36202-208 rhodium complexes, 36:219 imino substituent, 36:204-208 titanium complexes, 36.218 modes, 36202 NSN cumulene, 36202-204 Sulfur dioxide, insertion reactions, 12:33- platinum, 36:204 70,22150 pnicogeno substitution, 36205-208 with u-allyls, l2:52-56 tungsten, 36203 chromium, molybdenum, and tungsten, coordination reactions 1260-61 fragmentation, 36208-212 cobalt and rhodium, 12:66-68 hydtides. 36212-215 with cyclopropyl complexes, 1257-58 a-organyl complexes, 36215-216 gold, a70 osmium-mediated cleavage, 36216 intermolecular, 12:35 ruthenium, 36215 intramolecular, 1235 hydrido-benzochalcogenadiazole com- iron and ruthenium, 1263-65 plexes, 36214 manganese and rhenium, 1262-63 hydrotungstenation, 36:213 mechanism, 12:38-50 interactions, 36211 into metal-carbon a-bonds, 1236 Sulfur dioxide into metal-oxygen bonds, U:36 addition to nickel, palladium, and platinum, l268-70 coordinated ligands, U:36 in organic solvents, a44 metals, a36 with propargyl complexes, D.56-57 cycloaddition to bonded hydrocarbons, stereochemistry of products, 12:46-48 12:36 thermodynamic data, 1245-46 insertion with tin complexes, a58 into Group VI metal-metal bonds, titanium and zirconium, 1259 18: 15 into transition metal-Group IVB metal into iron-carbon bonds, stereochemis- bonds, a36 try, 18156. 180-182 into transition metal-transition metal reaction with bonds, 12:36 Sulfur-nitrogen-phosphorus polymers 302

Sulfur-nitrogen-phosphorus polymers, effect of polymer cross-linking, 32133 15210-211 Sulfur oxides, insertion reactions, 5:230, and nature of metal complex, 15:212 248-249,293 and nature of solvent, 15211 Sulfur-silene adducts, 39132 and nature of support, 15210 Sulfur-substituted carbene complexes hydrosilylation, 15213-218 reactivity effect of surface area of support, carbene ligand rearrangement, 25155 15216 nucleophilic substitution reactions at mechanism, 15213-216 Ca, 25149-153 specificity, 15216-217 oxidative addition reactions, introduction of metal, 15202-205 25154-155 via bridge splitting reactions, 15204 spectroscopic properties, 25149 by ligand displacement, 15203-204 structure, 25146-148 via oxidative addition of support to synthesis, 25135-146 metal, 15205 Sulfur trioxide, insertion into metal-carbon by reaction of metal halide with sup- bonds, l2:72 port, 15202-203 Sultines, desulfination reactions, 12:57, via reductive reactions, 15205 61-62 olefin isomerization, 15226, 228, 291 Sultone complexes, a72 oligomerization of acetylenes, 15224-226 Superconductivity, of graphite intercalation oxidative acetylation, 15228 compounds, 2893 oxidative hydrosilylation of olefins, Supercritical water, 38184 15228 Supersilyl group, 37:34 polymerization, 15226-227 Supported catalysts on polystyrene, 15197-201 for hydroformylation, 1247-53 direct binding to metals, 15201 for hydrogenation, 12361-367 phosphinated derivatives, 15197-200 cluster species, 12372 sulfonated derivatives, E200 nickel complexes, 17:235 preparation of support, 15193-205 for hydrosilation, 12408, 415 selectivity, 15192-193 for methanol carbonylation, 17:262-264 in sequential reactions, 15228-230 rhodium complexes, 12262-264 on silica, 15194-196 for tclonierization of butadiene, 12157 Supracyclopentadienes, synthesis of, palladium complexes, 12157 33300-310 Supported transition metal complex cata- Supramolecular-medium effects, homoge- lysts, 15189-231 neous catalysis, 38181-182 on alumina, 15196 Surface compounds, 2889-90 carhonylation of ally1 chloride, 15223 Surface-supported triosmium clusters, as conversion of acylchlorides to ketones, catalysts, 26:63-65 15224 Surface tension, AsSi-silicates, 4227 cyclooligomerization, 15239 Switching frequency, alkali radical ion com- of butadiene, 15218, 226 plexes, 2152 ethylene dimerization, 15224 SYBYL force field, 36:129-130 hydroformylation, 15218-223,239-240 Symmetry linear vs. branched chain products, elements, k243-246, 249-250 15218-219 of cyclic hydrocarbons, k254-255 mechanism, 15:222-223 operations, 1:244-246 hydrogenation, 15205-213 Synthesis comparison with homogeneous cata- acetylcarbonyl-$-cyclopentadiene-~5- lysts, 15212 cyclopentadienylmolybdenum, 26:337 Synthesis

acetylcarbonyl-~cyclopentadienyl-~4- cyclopentadienylindium complexes, dienetungsten complexes, 26341 26250 acyclic oxapentadienyl transition metal cyclopentadienyl(pentadieny1)iridium cat- complexes, 26:155-156 ions, 26152-153 acyclic pentadienylmetal complexes, cyclopentadienyl(pentadieny1)rhodium 26126-127,130-131, 136 cations, 26:152-153 acyclic pentadienyl-transition metal com- cyclopentadienylthallium complexes, plexes, 26136,153-155 26252-253 from alkynes, 26154-155 cyclopentadienyltin cations, a275 by oxidative addition, 26153-154 cyclopentadienyltin halides, 26274 acyclic pentadienyltricarbonylmanganese decamethyldicyclopentadienylsilicon, complexes, 26149-150 26288 alkylidynetungsten compounds, 2698 11-deoxyanthracycline antibiotics, 26:134 26241 alkynylaluminum complexes, dialkylcyclopentadienylaluminum com- 26244 alkynylgallium complexes, plexes, 26:243 arene complexes of lead, 26281 dicarba-closo-decaborane icosahedrons, T 26278 arene complexes of tin, 26240 arenegallium complexes, 26247-248 dicarbollylaluminum complexes, 26244 @"-benzocycloheptenedicar- dicarbollyllead complexes, 26281 bonyltrimethylphosphitechromium, 26:276 26323 dicarbollyltin complexes, dicyclopentadienylgermanium, 26:258 binary pentadienylmetal complexes, 26135-136 dicyclopentadienylgermanium complexes, 26258 bis(tetrahydr0furan) adducts of cyclopen- 26279 tadienylmagnesiurn complexes, dicyclopentadienyllead complexes, 26232 dicyclopentadienylmagnesium complexes, bridged triosmium clusters 26232 double-atom bridged, 2616 dicyclopentadienyltin, 26268 single-atom bridged, %14-15 dicyclopentadienyltin complexes, triple-atom bridged, 2617 26268-269 n-carbollylboron complexes, 26240 ~~-dienemetal carbonyls carbollyl complexes of Group VB metals, of chromium, 26298-299 26283 of molybdenum, 26299 carbollyl complexes of Group VI ele- of tungsten, 26299-300 ments, 26285 dimethylpropynylindium, 26248 carbollylgermanium complexes, 26266 disubstituted $-diene metal carbonyl chloro(pentarnethylcyclopentadieny1)- complexes, 26300 methylaluminum, 26243 ditungstacyclobutadiene, 2699-100 cross-conjugated dienyltricarbonyliron cat- dodecacarbonyltriosmium, 26:39-41 ions, 26148 dodecacarbonyltriosmium derivatives, cyclopentadienylberyllium complexes, 2644-45 26228 electrochemical, see Electrochemical syn- cyclopentadienylboron rt complexes, thesis 26238 electron-deficient $-dienechromium com- cyclopentadienyl complexes of phospho- plexes, 26315-316 rus, arsenic, and antimony, 26282 l-ethyl-l-alumino-2,3-dicarba-cZoso- cyclopentadienylgalliurn complexes, dodecaborane, 26243-244 26246 five-membered metallacycle, computer cyclopentadienylgermanium cations, representation, 26184-185 26265 four-membered metallacycle, %187 Synthesis 304

l-germa-2,3-dicarba-closo-dodecaborane, deca-3,5,9-trienechromium, 26267 26326-327 homodienylic alcohols, 26134 tri~arbonyl-q~~-bi-cyclo[4.4.llundeca- mixed-metal triosmium clusters, 26:71-81 2,4,8-trienechromium complexes, from dihydriododecacarbonyltrios- 26326 mium, 2671-73 trienerhodium complexes, 26153 of gold, 2W3-75 1,3,5-trienes, 26133 by oxidative addition of metal hy- 3-triethylsilyoxypentadienyllithium, drides, 2671-72 26133 unbridged tetrahedral clusters, 2679 trimethylenemethane metal complexes, mixed-substituted germanocenes, 26258 22279-289 mixed transition metal carbollylgerman- trimethylsilylstannacarboranes, 26:277 ium complexes, 26:266 Synthesis, carboxylic acids, 840 mixed transition metal cyclopentadienylg- cyclic hydrocarbons, 848-74 crmanium complexes, 26264 cyclododecatrienes, 835 molybdenum and tungsten alkoxides cyclononanes, 8:35 carbonyl complexes, 22359-360 cyclooctenes, 834 cis-hexa-2,5-dienoate, 841-42 dinuclear alkyl and aryl complexes, lactones, 843-44, 46 22344-346 Synthesis gas dinuclear alkyne complexes, in ethylene glycol production, 1280-83 22337-339 manganesepentacarbonyl alkyl reaction, isonitrile complexes, 22362-363 32202-204 metallacyclobutadiene complexes, Szilard-Chalmers reaction, 1k207-216 22330-333 mononuclear alkylidene complexes, 22312-314,316-317 T mononuclear alkylidyne complexes, 22320-323 Taft-Dubois steric parameter, X128 polynuclear alkylidyne complexes, Taft steric parameter, E'\, 36134-136 22353-355 [TaH( q2-S=C(R)H)(q5-C5Me&1, re- arrangement reactions, 43178 monocyclopentadienylead complexes, TAMREAC, see Transition metal reactiv- 26281 ity, computer program mono-?r-cyclopentadienylmagnesiumcom- Tantalum pounds, 26232-233 cyclopentadienyl isocyanides, 22231-232 pentadienyl-alkali metal complexes, metallacycles, 26:100-102, 190 26127 photoelectron spectrum, 26103 q3-pentadienyl-transition metal com- pentaalkyls, 14238-239 plexes, 26141-143 pentacarbonylmetallate anion, see Penta- q'.pentadienyltricarbonyliron cations, carbonylmetallatc(3-) of niobium 26144-147 and tantalum pentadienyltricarbonylmolybdenum Tantalum alkyls, "C NMR spectra, anion, 26151 19264-265 pentamethylcyclopentadienylgermanium Tantalum, carbene complexes, 20197 chloride, 26262 alkylidene transfer to carboxylic acids, ruthcnocenes, 26137-138 20:222 stannocenophanes, 26:268 "C NMR spectrum, 20212 terpenes, 26132-133 decomposition of cyclopentadienyl, transition metal carbynes, 2756-69 1R461-465 tricarbonyl-q4 Z-hi-cyclo[6.3.2.02.'] tri- M-C bond polarization, 12462 305 Tellurium transition metal complex

Tantalum carbonyls, 2182 sodium salt, 2203 Tantalum, carbyne complexes complexes, 8239-240 reactions, with acetylenes, 2291 anionic hydride, spectroscopic proper- structure, 2754 ties, 228, 21 synthesis, 2759-61 arene, 1365, 91 Tantalum complexes compounds, radiochemical synthesis, agostic neopentyl, 28321-322 11232 anionic hydride, spectroscopic properties, electron-transfer reactions of carbonyl 224 phosphine halides, 2321 arene, 1360-61 Technitiumpentacarbonyl alkyls, 37:170 benzyne Telechelic polymers, 1857-58 reactivity, 42167 carboxylated, l8:YO synthesis, 42165-167 synthesis via organolithium catalysts, bis(cyclopentadieny1) carbonlylalkyl, mi- 1889-93 gratory insertion reactions, 26:189 thiolated, 1890 carbene redistribution reactions, 23126 Telluradigermiranes, 39302 $-CH, 30184 y-Tellurido dialanes, 3944 electron-transfer reactions Tellurium cyclopentadienyls, 2346 biomethylation, 20327 seven-coordinate carbonyls, 235 71 complexes, 26:285-286 organolithiumcarbyne derivatives, 24:409 reaction with phosphasilenes, 39:211 photochemistry terphenyl derivatives, 4456 bis(cyclopentadieny1)alkyl halide, Tellurium mixed transition metal complex 24273-274 cobalt and molybdenum, 3k175 bis(cyclopentadienyl)dimethyl, iron 24~271-273 cobalt and rhodium, 31:172-173 cyclopentadienylbenzyl dichloride, manganese, 31172 24215 molybdenum, 3k169-171 trimethylenemethanc, synthesis, 27:283 nickel, palladium, and platinum, 31:173 122-valence electron, 30204 ruthenium and osmium, 31172 128-valence electron, 30201-204 structure, 31169-170 130-valence electron, 30200-201 thermolysis, 31170 ylide, 14207, 238-239 Tellurium transition metal complex mechanism of formation, 14239 bond length, 31160-161,164 X-ray structural studies, 14239 chromium, molybdenum, and tungsten, Tautomerisni 31155-157 metallotropic, 1021 antimony comparison, 31156 in organometallic compounds, 1015 ditellurium moiety, 31156 valence, see Valence tautomerism geometry, 31155 Tebbe’s reagent, 34140-141 reactivity, 3k15.5 methylenation reaction, 201 96-197, Zintl-type, 3k157 221-222 cobalt and rhodium 167-168 of esters and lactones, 20221 cluster, 31167 of ketones, 20196-197 resonance structure, 31168 methyl exchange, 20195 iron, ruthenium, and osmium, 31165-167 in olefin homologation, 20195 cubic cluster, 31:167 reaction with acetylenes, 20219-221 dimetalla-ditelluride, 3k165 Technetium ditellurium ligand, 31165 carbonyl anionic derivatives, 2202 heterometallic species, 3k166 hydride, 22055206 hydride cluster, 31:166-167 Tellurium transition metal complex 306

triply-bridged species, 3k166 Terphenyl ligands manganese and rhenium, 3k157-165 Be compounds, &lo-12 bonding, 3k158-159, 162 d-block, transition metal, derivatives, cationic species, 3k164 U14-17 dimetalla-ditelluride, 3k163 Group 12 elements, 44:18 semiconductor material, 3k164 Mg compounds, M13-14 six-electron donor ligand, 3k162 p-block elements, a18-19 trimetal, 3k159 A1 compounds, 44.23-25 nickel and platinum, 3k168-169 As compounds, U45-47 dicationic species, 3M69 B compounds, M19-23 phosphine, 31:168 Bi compounds, U47-50 spectroscopic study, 3k175-176 C compounds, a31-32 IZ5 Te Mossbauer, 31:176 In compounds, &30 '*' Te NMR, 31:175-176 Ga compounds, @25-27,29 zirconium and vanadium, 3k154-155 Ge compounds, &33-39 Telluroaldehyde compounds, see Heteroal- Group 17 derivatives, &56-58 dehyde transition metal complexes N compounds, &39-41 Tellurocarbonyl compounds, see Heteroket- 0 compounds, 4450, 52 one transition metal complexes Pb compounds, 4453-39 Tellurolatcs, multiple bonding, 39:44-47 P compounds, &41-45 Telomerization of butadiene Sb compounds, a47 nickel catalyzed, 12143, 146 S compounds, 4452-55 palladium catalyzed, 12145-146, 151-168 Se compounds, M55-56 use in natural product synthesis, Si compounds, U32-33 12182-189 Sn compounds, &33-39 of acetoacetate telomers, 17A87-188 Te compounds, 4456 of acetoxyoctadienes, 12182-184 T1 compounds, M30 of malonate telomers, 12187 phenolate derivatives, 44:3-6 of nitroalkane telomers, 12184-187 Terphenyl thioaminyls, oxidation, M41 of nonadienonate, 12188-189 Terphenylthiols, synthesis, 4452-55 Telomerization of isoprene, 12168-172 Tertiary phosphines, in aqueous solution, asymmetric, 12170 38164-166 head-to-tail, 12169, 171 Tertiary phosphine-transition metal com- regiospecificity, 12168, 170 plexes, 38166 Temperature, bulk, see Bulk temperature chiral, 38179-181 Terbium, dimeric bid (cyclopentadienyl) hy- hydroformylation, catalytic, 3fk173-178 dride, 24A4.5 hydrogenation, catalytic, 38173-175, Terminal metal-alkynyl complexes, 38:90- 178- 179 99, 103 Tertiary stibines, 14197-202 Terpenes, 26:132-133 asymmetric species, 14198-200 Terphenolates rate of pyramidal inversion, 14199-200 associated chemistry, M14-17 cleavage of Sb-phenyl bonds, 14197-198 zinc derivatives, 44:3 quaternization, 14200 Terphenolthiolates, associated chemistry, resolution of asymmetric salts, 14200 M14-17 reactions Terphenylarsenic chlorides, reactivity, of ally1 compounds with CpFe(CO),Cl, 44-45-46 14:202 Terphenylbenzene, bromination, 4456-58 with metal carbonyls, 14200-202 Terphenyl derivatives, s-block elements, synthesis, 14197-198 M6-9 Tetraalklyllead compounds, 3860 307 Tetracyanoethylene

Tetraalkoxydiborons, 10249 acylation, 3k13 Tetraalkylboronates, with alkylating agents, with alkylating agent 2302-303 1,4-butaneditosylate, 3k12 Tetraalkyldisilenes, 39240 complex stability, 3k11 1,1,2,2-Tetraalkyldistannanes,38193 ethylating, 3k12 Tetraalkyl-Group 111 anions, 8:196-198 1R spectrum, 31:ll-12 Tetraaryldialuminum compounds, 398 methylating, 31:lO-11 Tetraaryldiaryldisilenes, 39255 characterization, IR spectrum, 3k5-8 Tetraaryldigallium compounds, 39:8 first row transition metal carbonyl com- Tetraaryldigennane, 39303 parison, 3k7 Tetraaryldigermasilenes, spectroscopy, hexamethylphosphoric triamide solu- 39285 tion, 3k5-6 Tetraaryldigermenes, 39285,290 ruthenium complex comparison, 31:5-6 Tetraaryldiindium compounds, 39:8 sodium-manganese interaction, evi- Tetraaryldisilenes, 39237,249, 253 dence, 31:s Tetrabenzometallepins, 13223 "C NMR study, 3k4 arsenic, 13:223 conductivity study, 31:8 Tetraboracyclooctane, 2318 with main group electrophile, 3k10-13 Tetraboranes dianion, 31:lO-11 alkyl derivatives, 3:294-295 octahedral, 3k10 CO complex, 3:295-297 seven-coordinate, 3k10 2,2,3,3-Tetrabromo-l,4-di-tert-butyl-l,1,4,4- protonation evidence, 3k8-10 tetramethyltetrasilane, 37A4 conversion to dihydride, 3k9 Tetrabromodisilane, 3234 'H NMR spectrum, 3k8-9 Tetra-t-butyldisilene, 39255 IR spectrum, 3k8-9 1,2,3,4-Tetra-rert-butyl-l,2,3,4- structure of dihydride, 31:lO tetrachlorocyclotetragermane, 329 trihydride, 3k10 1,2,3,4-Tetra-tert-butyI-l,2,3,4- synthesis, 3k2-5 tetrachlorocyclotetrasilane, 3211,16 thermal stability, 31:4 1.2.3,4-Tetra-tert-butyl-1,2,3,4- with transition metal electophile, tetraphenylcyclotetragennane, 328-9 31:14-15 1,2,3,4-Tetra-fert-butyl-l,2,3,4- complex structure, 3k14-15 tetra(phenyl)cyclotetrasilane, 37:ll triphenylphosphinegoId(1)chloride, Tetra (t-butyl) tin, 38192 3k14 2,3,4,5-Tetracarbahexaboranes,39357, 384 Tetracarbonylnickel, 26:154 Tetracarbonyl-2-(acetyl)ferrocenyl man- Tetracarbonyl(tripheny1phosphite)manga- ganes, 37:205 nate(-I) and hexacarbonylman- Tetracarbonylmetallate(4-) anion of chro- ganese(I), 3374-75 mium, molybdenum, and tungsten Tetrachlorocyclotetragermane, synthesis of characterization, 3k40-42 precursor, 328-11 IR spectrum, 3k40-41 Tetrachlorocyclotetrasilane, synthesis of pre- derivative, 31:42-45 cursor, 3211-12 carbonylhydrido cluster, 3k44-45 Tetrachlorodisilane, 3%23 diamine, 3k42 Tetrachlorogennane, 3218 dianion, 3k44 1,2,3,4-Tetrachloro-l,2,3,4-tetra(l-ethyl-l- hydride, 3k42-43 meth ylpropyl)cyclotetragennane, tiphenyltin, 3k42 37:lO-11 synthesis, 31:39-40 Tetracyanochinodimethane alkali metal Tetracarbonylmetallate(3-) anion of manga- compounds, structural data, 27:245 nese and rhenium Tetracyanoethylene Tetracyanoethylene 308

1,3-addition to q4-dienes, 1529 his adducts of cyclopentadienylmagnes- insertion into metal-carbon bonds, U71 ium compounds, 26:232-233 reactions with dicarbollylaluminum adducts, W244 isocyanide complexes, 1k66 interaction with graphite intercalation phenylethynylcopper, 12289 compounds, 28:97-98 Tetraeyelo[3.3.02~’.0?.h]octasilane,3211 tris adducts of cyclopentadienylmagnes- Tetra-decker sandwich complexes ium complexes, 26:233, 236 bonding, 18306.334-336 Tetrahydrofuran-iminosilane adducts, of 1,2.5-thiadiborolenes, 18334-336 39167-170,179-180 Tetradehydrobenzene, transition-metal com- Tetrahydrophosphinines, synthesis with pho- plexes, 42175 sphaalkenes, 4k22-24 Tetra(difluoromethy1ene) metal complexes, Tetrahydropyrroloquinolines,synthesis, 3~29,36 42:162 Tetracthyllead, 1313 1,2,3,4-Tetrahydro-l,2,3,4-tetraborete, @-decay, 11:208,234 39380 industrial synthesis, 3868-69 Tetrakis[bis( trimethylsilyl)methyl]distanene, X-irradiation, 1k212 39311,316, 318 1,2,3,4-Tetra(l-ethyl-l-methylpropyl)- Tetrakis (dialkylamino) diborons, reactions, 1,2,3,4-tetraphenylcyclotetragermane, 10242 321 1 Tetrakis(2,6-diethylphenyl)digermene, Tetrafluoroboranation, methyl rheniumpen- 39295,299, 301-303 tacarbonyl, 32208-209 Tetrakis(2,6-diisopropylphenyl)digermene, 39:238 Telrafiuoroboric acid, 3227,39301,303 Tctrafluoroethylene Tetrakis(3-methy1pentadienyl)trimanga- methyl rheniumpentacarbonyl reaction, 26137 3221 2 nese, Tetrakis (trialkylsilyl) disilene, reduction re- reaction with metal carbonyls, k180 action, 3828 Tetrahalodiboranes(4), 10242 Tetrakis(trialkylsilyl)disilenes, 39236, addition to acetylenes and olefins, 10251-253 241-242 Tetrakis(2,4,6-triisopropylphenyI)- alkylation, 10246-247 aromatic hydrocarbons, 10260 digermene, 39295 ferrocene, 10263 Tetrakis(2,4,6-triisopropylphcnyl)- haloolcfins, 10257-260 distannene, 39315-316,318 metathetical reactions. 10242-247 Tetrakis (trimethylsilyl) silane, 3828 organo-Group IV compounds, 10241 Tetrakis(tri-terf-butylsi1yl)tricyclo- thermal decomposition, 10250 [I. 1.0.02,4]tetrasilane,3234-35 Tetrahalogenocyclobutanes, 326 Tetralithiosilane, 3817 Tetrahalogenodisilanes, 37:14 2,2,4,4-Tetramesityldigerma-1,3-dioxetane, Tetrahedranes, 321 39299 precursors, 326 Tetramesityldigermene, 39287,295, 297, tetrasilatetrahedrane, 321-4,8, 34-36 301,303 Tetrahydroborate ligand reactions, 39299-300,303 ally1 analogy, 2k84 Tetramesityldisilene, 3996,212, 223

bonding modes, 2k85 Tetramesitylgermasilene, reactions, 39291 ~ metal complexes, 2k59,85-86 292, 297,299, 303 molybdenum tetracarbonyl anion, 2M36 1,1,2,2-Tetramesityl-3-phenyldisilacyclobut- Tetrahydroborates, organosubstituted, 3-ene, 39:212 3292-294 Tetramethoxysilane, DEPT and INEPT Tetrahydrofuran spectra, 23202-204 309 Tetrazenes

2,2’5,5’-Tetramethylbiarsole,conformation, mechanisms, 16328-329 39339-340 mixed metal species, 16329 Tetramethylbis(p-phenylethynyl)digallium, of rhodium, 16328 26:244-245 Tetraorganodialane, 397-8 Tetramethylbis(p-propynyl)digallium, Tetraorganodiboron compounds, 397-8 26244-246 Tetraorganodimetallanes, 397-13 Tetramethylcyclobutadiene nickel chloride 1,1,2,2-Tetraorganodistannanes,38205 structure, 4100 Tetraphenylarsacymantrene, 39333, 350 2.2‘ 5.5 ‘-Tetramethyl-1,1 ’-diarsaferrocene, Tetraphenylcyclobutadiene iron tricarbonyl, reactions, 39347 structure, 4:YY-100 3,3’,4.4’-Tetramethyl-l ,l’-diarsaferrocene, Tetraphenylcyclopentadiene 39332, 339, 345 stabilization, 33319-323 2,2’ ,5,5’-Tetramethyl-l,1 ‘-dibismaferro- synthesis of, 33301-302 cene, 39328 2,2‘,5,5’-TetraphenyLl,l’-diphosphaferro- 2,2’,5,5’-Tetramethyl-l ,l’-diheteroferro- cene, reactions, 39345, 347 cenes, electrochemistry, 39343-344 Tetraphenylethylene, 2814 Tetramethyldiphenyldisilane, a25 2,3,4,5-Tetraphenylsarsaferrocene,39:332 Tetramethyldisilene, 39239 1,3,5,7-Tetraphoisphabarralene,synthesis Tetramethyldisiloxane, catalyzed dispropor- with phosphaalkynes, 4k55 tionation, 19235-239 Tetraphosphacubanes, synthesis with phos- Tetramethyl-1,l ’-distibaferrocene, 39327, phaalkynes, 4k.55,57-58, 61 332,347 Tetraphosphanobornadiene, synthesis with 2,2’,5,5‘-Tetramethyl-1 ,l’-distibaferrocene, phosphaalkynes, 4k59 reactions, 39947 1.2,3,4,5-TetraselenagermoIanes,39290 3,3’,4,4’-Tetramethyl-l,1’-distibaferrocene, Tetrasilacyclobutadiene, 37:35-36 reactions, 39348 Tetrasilane, 3836-37 Tetramethylethylenediamine Tetrasilatetrahedrane, 37A-2, 8, 34-36 cyclopentadienyl magnesium bromide ad- theoretical studies, 322-4 duct, 26233 Tetrasilyldigermene, reaction with 1,3- fluorenylpotassium complex, 26224-225 dienes, 44:136 idenyllithium adduct, 26218, 225 Tetrastannanes, 38205-211 triphenylmethylsodium complex, 26224 Tetrasulfur, insertion into cobalt-carbon tris(trimethylsilyl)cyclopentadienyl(meth- bond, U:75 y1)magnesium complex, 26:233 1,2,3,4,5-Tetrathiagermolanes,39290 1 ,1’,2,2’-Tetramethylferrocene,39:348 Tetrazenes, derivatives of Group IV ele- 2,3,4,5-Tetramethyl-l-phenylbismole,39330 ments 2,3,4,5-Tetramethyl-l-phenylstibole,39330, electronic structure, 24.213 340 energy levels for trans geometry, Tetramethylsilane, as reference for ”C 24213-214 NMR spectra, l2139-140 MO calculations, M214 Tetramethyltetraphenylcyclotetrasilanes, photoelectron spectra, 24214 3837 ultraviolet spectra, 24214 Tetramethyltin, 320 geometric structures, 24207, 212-213 preparation, 3869 isomerization, 2215-219 Tetramthylsilane, DEPT and INEPT spec- hindered rotation, 24215 tra, 23:198-202 1,3-migrations, 24:216-219 1,1,3,3-TetranmethylindanteIlone,isolation, 1,4-migrations, M217-219 43126 substituent effects, 24.217 Tetranuclear carbonyl clusters, molecular re- thermal cis-trans rearrangements, arrangements, 16328-330 24216 Tetrazenes 31 0

lithiated derivatives chromium complexes, 3957 and arsenic halides, 24241, 243 heterocarborane and beryllium chloride, 2240-241 structure, 30106 and boron bromide, 2240-241 synthetic precursor. 30106 and carbon tetrahalides, 24241-243 iron complexes, 39:59-60 and nitrogen halides, 24245 multiple bonding, 39:2 and phosphorus halides, 2241, in organic chemistry, 1k147-202 243-244 terphenyl derivatives, 44.30 reactions, 24:240-245 tetraorganodimetallanes, 39:6-13 and sulfur halides, 24241, 244 transition metal complexes, 3948-4Y synthesis, 24293 Thallium amides, 39:18 'H NMR spectra, 24209, 211 Thallium compounds oxidation, 24233-234 biomethylation, 20330 formation of radical cation, W.234 borane, 2k66 photolytic radical decomposition, molybdenum, 3%53 24215-216 organometallic, 393 preparation, 24202-207 reaction with methylcobalamin, 20:320 via cycloaddition reactions, 24204-205, substituted cyclopentadienyls, 21:5-6, 12, 210 17-18, 26-28,34,38,44-45 from diazenes, 2203 Thallium cyclopentadienidc, 2370-371, 373, from hydrazides and diazonium salts, 1M4Y 24:204 nitrogen chain building, 24:202-205 derivatives, 1k151-155 Thallium, n via protolysis, 2205 complexes by substituent exchange, 2205-207 alkyne complexes, 26252 reduction, M234 of tin anions, 26.255-257 substitution reactions, 2235-246 of bonding, 26256 of hrydrogen, 24:238-239 reaction with phosphonium or protolysis, 24:23.5-237 arsonium cations, 26256 substituent exchange, 2237-238 arene complexes, 26257, 287 thermolysis, 24:207, 219-233 cyclopentadienyl complexes, 26252-255 acyclic compounds, 24219-231 structures, 26:254 cyclic species, 24:232-233 with transition metal sandwich, 26256 disubstituted derivatives, 24228-230 Thallium(1) halides, reactions with Grig- fully substituted derivatives, nard or organo-lithium reagents, 1k148 24220-228 Thallium(II1) acetate, reaction with olefins, mechanisms, 2219-220 5240 monosubstituted derivatives, 2230 Thallium(I11)-catalyzed oxidation of 2-hex- organyltetrazenes, 24230-231 ene, 16254-255 trisubstituted derivatives, 24238 mechanism, 16254-255 Tetrazole complexes, from azides and isocy- Thallium(II1) nitrate, 11:187 anide complexes, 1k41 as an oxidizing agent, 1k187-202 Thallation rcactions, 1k161-202 acetylenes, 1k191-194 isomer distribution, 11:166 aldehydes and ketones, 1klY5 kinetic studies, 1k168 chalcones, 11:18Y orientation dependence on reaction condi- cyclohexanone, 1lAY5-198 tions, 1M69 enamines, 1k200 reversibility, 1k165 enolized carbonyl compounds, 1k19Y Thallinium ions, 1k183-185 p-keto esters, 1k201 Thallium olefins, 1k187 31 1

Thallium(II1) organic compounds, polyhalogenoarenecarboxylates,metal, 1k155-202 25248-254 alkyl derivatives, 1k173 main group element compounds, conversion 25252-254 to aryl iodides, 1k158 transition metal derivatives, 25248-251 to phenols, 1k159 Thermal decomposition formation from organocobalt complexes, heterocycles, 44:153-156 1k424 importance in organometallic mass spec- preparation tra, 8212 (R,TI), 1k155-156 ketene complexes, 2848-49 (R*TIX), 1k156-158 transition metal alkyls (aryls), 2186-187 (RTlXZ), 11:160-163 Thermal extrusion, in synthesis of trimethyl- Thallium(II1) salts, as oxidants, 1k174 enemethyl metal complexes, Thallium(II1) trifluoroacetate, 11:163-173 22282-283 kinetic studies, 1k168 Thermal isomerizations, boron compounds, as thallation reagent, 1k163 2261-265 Theoretical studies Thermal reactions, in radiochemistry, acetylene complexes, l520-21 11:238 bent sandwich complexes, 1534-37 Thermal stability, silenes, 3995 photoelectron spectra, 1534 Thermal synthesis, of silenes, 257-9 bridged electron-deficient beryllium com- Thermochemistry, of organoarsenic com- pounds, 15255 pounds, 4228-229 butadiene complexes, 1527-30 Thermochromism, 3077 structures, 1527 disilenes, stable, 39241 and Woodward-Hoffmann rules, 1528-29 Thermodynamics nucleophile-carbonyl adduct formation, cluster compounds, l540-45 28160- 166 fluoroolefin complexes, 1525-27 2397-99 Group IVB radical anions, 15298-305 redistribution reactions, metal-metal bonded complexes, 1537-45 Thermolysis olefin complexes, 1514-27 arsasilenes, 39222-223 stability, 1524-27 aryldisilane, 3974,80 structure, 1519-24 1,l-dimethyl-1-silacyclobutane,3972 organometallic compounds, 151-45 disilylalkynes, 3974,80 pentatienyl complexes, 1530-31 (fluorostannyl)silylphosphine,39310 metal tricarbonyls, l530 4-germa-l-pyrazoline, 39294 sandwich complexes, 1531-34 germenes, el23 Thermal decarboxylation hexamesitylcyclotrigermane, 39287,300 alkenoates, metal, 25247-248 hexamesitylsiladigermirane, 39287 alkoxycarbonylmetal compounds, 25265 lithium(fluorosilyl)phosphanylides, 39198 alkynoates, metal, 25247-248 phosphasilenes, 39209-210 arene- and heteroarenedicarboxylates, 1,2-phosphasiletane, 39197 metal, 25258-263 polysilane, 3974,80 arenecarboxylates, metal, 25254-257 polysilylalkynes, 3974,80 carborane carboxylates, metal, 25264 silacyclobutanes, 3973-75,106 cyanoacetates, metal, 25246 silene preparation, 39140 heteroarenecarboxylates, metal, 1-(2,4,6-tri-t-butylphenyl)-2,2- 25257-258 dimesitylgermaphosphene, polyhalogenoalkanoates, metal, 39303-304 25243-246 1,2,5-Thiadiborolenes, 18311-312 1,2,5-Thiadiborolenes 31 2

boron-carbon bond length and complex- Thio-2,4,6-triphenylaniline compounds, syn- ation, 18312 thesis, 44:40 metal complexes, 18311-314 Third-order optical nonlinearity hinuclear, 18:324-325 computational calculations, 43367 tetra-decker sandwiches, 18334-336 experimental techniques triple-decker sandwiches, 18326-327, comparison of results between tech- 332-333 niques, 43366-367 potassium reduction, 18312 degenerate four-wave mixing, Thiadigermiranes, 39302 43360-361 l-Thia-2,4-diphosphole, synthesis with phos- optical Kerr gate, 43363-365 phaalkynes, 4k45 power-dependent transmission, 43365 Thiadisiliranes, 39259-260 pump-probe technique, 43365-366 Thiasilanones, 39194 third harmonic generation, 43358, 360 1,3,4-Thiazadiphosphole,synthesis with pho- Z-scan, 43361-363 sphaalkenes, 4k18-19 optical power limiting, 43356-358, Thicarbonyl complex, and formation of thio- 398-401 formyl, 17:374-375 organometallic compounds Thioacyl, coordinated ligands, electrophilic third-order calculations, 43392, addition to, 25135-138 395-398 Thioaldehyde compounds, see Heteroalde- third-order measurements, 43368-394 processes, 43354-356 hyde transition metal complexes systems of units in expression of pro- Thiobenzophenone adduct, 39257 cesses, 43:358-359 Thioberyllium alkyls, 9236 theory, microscopic and macroscopic, Thiocarbene complexes, synthesis, 43352-354 4k224-225 Thorium cyclopentadienyl complexes Thiocarbenes, 3221-23 with hydrogen bridges, M169 Thiocarbonyl complexes, via metal atom photochemistry of alkyls, 24:250-253 synthcsis, 1564 Thorium cyclopentadienyls, 9:386-388 Thiocarbonyl compounds, insertion reac- cyclooctatetraene complex, 9388 tions, 5291-292 Thorpe-Ingold effect, and organo-Group I Thiocarbonyl ligands, reactions with elec- aryl migrations, 16191-192 trophiles. 2263-64 Three-center bonding Thiocumulenes, 39:316 boron, 30153 complexes, 10177-180 dinuclear metal complex, 3M75-179 Thiocyanates, src also Pseudohalides evidence, 30155-162 properties, 5211-214 isoelectronic complex, 30207-208 Thioethers, 3212-14 Si-H Thiolates, 3212-14 chromium complex, 30172-173 multiple bonding, 3944-47 iron complex, 30180-181 Thiollide (BIoHIOSZ) complexes, 8104 manganese complex, 30154-170 Thiols, reactions with unsaturated germa- 72-SiH and 772-CH comparison, nium compounds, 39:292 30182-184 Thiones, 323-12 Sn-H-Mn, 30:173-174 Thionitrosyl complexes, 22256 Thulium alkyls, a136 Thiophene, activation by transition by tran- Time-dependent phenomena, in NMR, sition metals, 32305-306 3156-161 Thiophenyl-group 10 metal complexes, Time-resolved IR spectroscopy third-order nonlinear optics, 43371, historical development, 25287-289 373-374 IR kinetic spectroscopy, 25289-298 31 3 Tin-Group 16 element heterocycles

CO lasers, 25291 reaction with methylcobalamin, 20320 in gas phase, 25292-295 redistribution equilibria, 6243-247 improved IR light sources, 25297-298 Tin-graphite, 28119-120 of solutions. 25295-296 Tin-Group 14 element heterocycles Tin homocyclic polytin compounds, anionic hydride complexes, spectroscopic 33183-185 properties, 224-5 bicyclo[2.2.0]hexastannane, 33185 applications of organotin compounds, cyclostannanes 43198-199 structural data, 33186 bipyridyl stannacarborane adduct, %244 synthetic routes to, 33184 carbon bond formation, see Carbon-tin rings, other heteroatoms, 33181-183 bond formation saturated heterocycles carbyne complexes, synthesis, 2269 ClSn[(CH2)8]3, 33177 cyclopentadienyl ruthenium complex, 1,3-distannacyclobutane,33174-175 3028-29 polystannacycloalkanes, 33:175-176 Mossbauer spectrometry of organic com- rings pounds, 921-134 more than one tin atom, 33:174-177 complex ions, 954 one tin atom, 33172-174 donor acceptor complexes, 953 stannacycloalkanes, 33173 isotope 119111, characteristics, 946 1,2,4,5-tetrastannacyclohexanes,33176 sources, 947-50 unsaturated heterocycles, 33178-1 81 organic derivatives, 447-63 Tin-Group 15 element heterocycles organoselenium derivatives, 582 tin-nitrogen heterocycles organosulfur derivatives, 554-57, 59-65, reaction mechanism, 33191 67-68,70,72-74,7842 reaction types, 33189-190 organotellurium derivatives, 582 phenylethynyl complexes, 38122, structural data, 33188-189 135-136 synthesis, 33187-188 terphenyl derivatives, 44:33-39 tin-phosphorus heterocycles tin-tin bond formation by dehydrogena- NMR data, 33193 tive coupling, 43:245 reactions, 33:192 transition metal complex, see Germa- Sn-P-C rings, synthesis, 33:195 nium, tin, and lead transition metal structures, 33:194 complex Tin-Group 16 element heterocycles in tnosrnium clusters, %69-70 no additional heteroatoms Tin compounds clusters, structures of, 33197 biomethylation, 20328-329 complex tin-rich rings, 33202-203 free radical mechanism, 20336 conformational isomerism, 33203 in sediments, 20:331 hydrolysis, 33199 cage and cluster, 321-14, 19-22 2,4,6-(Me2Sn),-1,3-Se2, 33205 double bonded, 39275-276 NMR data, 33200-201 properties, 39304-309 oligomerization, degree of, 33199 reactions, 39312-319 Ph3Sn02P(OPh)2,33206 spectroscopy, 39306-309 reaction chemistry, 33202 synthesis, 39309-312, 320 structural data, 33198 five-coordinate aryls, 20272-273 tin-X-carbon(X=O, S, Se, Te) via metal atom synthesis, 15107 diorganotin derivatives, 33214-216 nitrogen, 3413-439, see also Organotin- lattice structure, 33205 nitrogen compounds molecular structure, 33205 organometallic, bonding, 394 orthometallation reactions, 33214 Tin-Group 16 element heterocycles 31 4

polymeric compounds, formation of, cleavages, 459-63 33208-209 energy, 458 reaction chemistry, 33211-213 reactions, 459-63 solution state behavior, 33209-210 Tin, transition element heterocycles spectroscopic data, 33210 cobalt, 33224-225 synthesis, 33206-207 iron, 33221-224 unsaturated analogs, 33213-214 manganese, 33224-225 Tin heterocarborane, 301 16-127 osmium, 33222-223 atomic orbital sketch, 30121 ruthenium, 33222-223,225 bipyridine system, 30125-126 tungsten, 33226 bonding, 30120-126 Tin(I1) organic compounds, 19123-153 cage bond distance, 30120 anionic cyclopentadienyl, 19132 Lewis base adduct, 30124-125 q6 arene, 19126-128 reaction, 30126 arylalkoxy derivative, 19138 structure, 30119, 122-126, 139-140 bis(aryl), 19137-138 synthesis, 30:117-119 protolysis, 19140 tetradecker complex, 30139 bis(bistrimethylsilymethy1)amido analog, Tin hydrides, see also Organotin hydrides 19136 kinetic isotope effects, 44:103-104 metal carbonyl derivatives, 19139, reactions with 143-149 carbon-centered radical, U90-91, oxidative addition reactions, 94-99 19129-138 nitrogen-centered radical, M102 photoelectron spectrum, 19:141 oxygen-centered radical, 44:99, 101 photolysis, 19139 Tin isocyanides, 5184-185 spectroscopic properties, 19140-143 Tin methylhalides, and molecular com- structure, 19:136-137, 140-141 plexes, 1463-96 thermochromicity, 19140-3 41 Tin, nitrogen heterocycles carboranes, 19135,137 cyclic compounds, 33187 cyclopentadienyl halides, 19125,128 1,3,2,4-diazasilastannetidine,33190-191 mass spectra, 19132-133 Me2SnS2N2,schematic representation of, X-ray structure, 1912 33189 dicyclopentadienyls halides, 19125,128 reaction types, 33189-190 'H NMR spectrum, 19:133 structural data, 33188-189 as Lewis bases, 19128, 130 Tin, phosphorus heterocycles ligand exchange reactions, 19130 cyclic stannaphosphines, 33193 mass spectrum, 19132-133 MeloSn5P,, 33193-194 oxidation to tin(IV), 19129 Me12Sn6P,,33193-194 oxidative addition reactions, NMR data, 33193 19129-130 Sn-P-C rings, 33195 permethyl compound, 19126,128, Tin, II complexes 132-133 analogous to carbocations, 26:257 polymerization, 19128-129 arcne complexes, 26278-279 protolytic cleavage, 19131-132 cyclopentadienyl complexes, 26:267-276 reaction with diironnonacarbonyl, dicarbollyl complexes, 26:276-277 19147 mixed-metal sandwich complexes, 26:271, reaction with transition metal hydrides, 277-278 19131-132 Tin-sodium alloy, 3&69 relative stabilities, B129 Tin-tin bond, 38203-204,209-210.222- structures, 19124-126 223,235 and tcne, 19131 31 5 Titanium complexes

and tcnq, 19131 $-allyl, as hydrogenation catalyst, vibrational spectra, 19125 1937, 44-45 hexameric diphenyl, -135 aryl complexes, 1917 pentamethylcyclopentadienyl cation, binuclear p-q',$ C5H4 19:126-128 as acetylene polymerization catalyst, X-ray structure, 19126-127 1944 transition metal derivatives, 19143-149 and dehydrogenation of urea, base stabilization, 19144-146 19~33-34 reactions, 19147-148 functionally-substituted h-cyclopentadie- structure of Cr(C0)5 complex, nyl dicarbonyl complexes of Ti and 19143-145 Zr, preparation, 25345-346 synthesis, 19145-147 metallacycles, 2697 thermal rearrangement of iron car- Titanium complexes bonyl, 19148 acyclic pentadienyl, 26:136-137, 139 Tin-X-carbon heterocycles bonding parameters, 26140 aryl dithiolates, 33214-215 alkynyl, 3884 dioxastannolanes, 33209-211, 213 aluminum, 9162, 177 1,3-dioxastannolanes, 33:204, 206, 209 in catalysis, 9182-185 1,3-disubstituted-2-stannolanes, anionic hydride, spectroscopic properties, 218 33207-208 1,3,2-dithiastannolanes, 33208-209 arene, 1357-58, 64 as olefin polymerization catalysts, 1358 five membered, 33212-213 benzyne, synthesis, 42153-155 2,4,6-(Me,Sn)3-1,3-Se2,33205 bimetallic, 31257-258, 262-265, 278, 282, Ph3SnOzP(OPh)2, 33206 stannolanes,l,3-chalcogen-substituted, 295, 302-304 carbonyl diazene 33210 metal-induced bond cleavages, Titanium M93-94 ansa-titanocene dicarbonyl derivatives, metallacycles, 3494-95 preparation, 25343-344 carbonyl diazirine, 3495, 97-98 his( 77-cyclopentadieny1)dicarbonyl- as catalysts in Ziegler-Natta process, titanium, Cp2Ti(CO)zpreparation/ 16256-260 formation q2-CH, 30184 via other titanium complexes, chiral dicyclopentadienyl derivatives, 25331-333 18196 via reductive carbonylation of Cp,TiC1/ optical resolution, 18158-159 (CpzTiC1)z,25322-324 cyclopentadienyl as hydrogenation cata- via titanocene alkyl and aryl com- lyst, 11336 plexes, 25324-331 1,4-diaza-l,3-butadienes,2k170 his( 1)-pentamethylcyclopentadienyl) via metal atom synthesis, 1589 dicarbonyltitanium formation, octaethylporphyrin dioxygen adduct, 25336-338 16274-275 cationic carbonyls, 8:131 phosphaalkyne, 30:212-213 hydrogen complexes, 8213-214 phosphine-substituted cyclopentadienyls, ( 7)-CSMe5)CpM(CO), preparation, 25342 2k38 a-cyclopentadienyl derivatives, 1050, polymer-bound cyclopentadienyls, 384-388 2k46-48 cyclopentadienyltetracarbonyl(1-) anion, as catalysts, 2k48 3k19 reactions with dicyclopentadienyl derivatives, 19:l-50 bis(trimethylsilyl)diazene, 23183-187 Titanium complexes 31 6

carbon dioxide methyl trichloride, N258 alkyls, 22151 tetraalkyls, 24255-258 allyl, 22:162-163 neopentyl derivative, -257-258 redistribution reactions, 23106 norbornyl derivative, 24256-257 reduction of coordinated CO, 1272-73 Titanium compounds, organic $-SiH, 30175-177 in catalysis, 9182-188 tetrahydroborate, 21:63-64 nitrogen fixation, 9185-188 with thiazate ligands, 36:218 olefin polymerization, 9182-185 128-valence electron, 30:201-204 cyclooctatetraene complexes, 9180-181 in Ziegler-Natta catalysis phenanthroline, 9181 and aluminoxanes, 1tk140-143 polypyridyl derivatives, 9180-181 dicyclopcntadicnyls, 18124-129 Titanium, cyclopentadienyl complexes formation of dimetalated species. carhene, 20219-222 18131 dichloride with magnesium compounds, and dimethylzinc, m195 18120- 123 and trimethylaluminum, 20195 trihalide, 18113-120 metallacyclobutenes, 20:219-222 Titanium complexes, electron-transfer reac- p-methylenes tions p-chloro-aluminumdimethyl, see Teb- bis(arene) reduction. 2379 be’s reagent bridged bimetallics, 2498-Y9 paramagnetic p-chloride, 20246 cyclooctatetraene derivatives, 24.96-97 Titanium-graphite, 28126-128 cyclopentadienyls Titanium metallocyclc, 37:297-298 alkoxides, 2343 Titanium(T1) compounds, 9172-180 alkyls, 23:43-44 alkoxides, 9:173-174 bipyridyl derivatives, 2344-45 amido derivatives, 9173-174 cyclooctatetraene, 2366 P-diketonates, 9173-174 dihalides, 2341-43 halides, 9172-173 thiolates, 2343 phosphido derivatives, 9173 mediation by CO ligand, 23296 Titanium(I1) halides, addition complexes, Titanium complexes, photochemistry 9:172- 173 bis(cyclopentadienyl)alkyl halides, Titanium(II1) compounds 24268-269 alkoxides, 9144, 148-149 bis(cyclopentadienyl)dialkyls, 24259-264 amido derivatives, 9145, 151 with alkyncs, 24261 borohydride, 9145, 153 with CO, 24263 carboxylates, 9144, 149-1.50 with hydrogen, 24262 P-diketonates, 9144, 150-151 and methyl transfer to transition met- phosphido compounds, 9151 als, 24263-264 Titanium(II1) halide complexes, 9137-143 radical trapping, -260-26 I Group VI ligands, 9138-140, 143 with sulfur, 24263 Group V ligands, 9140-143 bis(cyclopentadienyl)diaryls, 24264-267 magnetic properties, 9147 with CO, N264 preparation, 9137, 146-147 with hydrogen. 24267 visible spectra, 9:147 pentamethylcyclopentadienyl deriva- Titanocenc, 9175-179 tivcs, -265-266 dinitrogen derivatives, 16272-274 and photocatalytic olefin hydrogena- Titanocene diacetylides, 37:257 tion, 24267 Titanoccnc dichloride, 32262,266,287, 295, reductive coupling of aryl ligands, 298 24264 reduction. 9:153 31 7 Transition metal allenyl complexes

supported on polystyrene, 15200 Trans effect, 12:9 and reduction of olefins, 15212 cr-alkyl groups, 2168 Titanocene monocarbonyl derivatives CO, and effect on carbonylation reaction, monocarbonyl h*-acetylene complexes, 12234 formation, 25358-361 correlation with direct metal-carbon cou- monocarhonyl-h2-olefin complexes forma- pling constants, l2:159-160 tion, 25361-364 ligands on reactivity of hydro group, monocarbonyl-phosphine complexes, for- 13305-306 mation, 23351-358 arsenic, 13:221-222 [T~(~-BT)(C~F~)~]~,arylation with, silicon, 13222-223 28226-227 mechanism, 1225 TMEDA, see Tetramethylethylenediamine in metal hydrides, 12.25-26 Tolane, 39332 NO vs. CO, 16:227 Tolman cone angle, 3697-104, 117-118, in organogold complexes, 20:92, 95, 99, 140, 142 102 Toluene, in gallium complexes, 26:245, 248 in platinum complexes, 1517-18 Toluene carrier gas, technique for bond dis- a,a-Transfer of ligands, 10375 sociation energies, 253-54 Transfer reactions, of organic groups from p-Tolyldiazomethane, cycloaddition reac- organocobalt complexes, 1k421-427 tion with disilenes, 39259 Transient species, organometallic o-Tolylmethylsilene, 39142 alternative methods for detection, Topology? and high nuclearity metal car- 25298-299 bony1 clusters, 14:337 detection by fast time-resolved IR spec- Tosyl azide, as source of diazo group, %399 troscopy TPM(CO)~- flash photolysis of metal carbonyls contact ion pairs, 33:91-93 in gas phase, 25283-284 electron transfer equilibria, 3393-96 in solutions, 29281-283 pyrylium cations, electron transfer be- unimolecular process, 25284-286 tween, 3389-91 low-temperature techniques spectral characterization, 3387-89 low-temperature solutions, 25280 TPPMS, 38173 matrix isolation, 25278-280 TPPMS complexes, 38174-175 time scales of reactions, 25286-287 TPPTS, 38163-164, 173-174 Transition metal alkyls, 32169-171 TPPTS complexes Transition metal alkyls and aryls, 7:157-204 as hydroformylation catalysts, 38:175-178 addition of mercury(I1) chloride, 2184 as hydrogenation catalysts. 38178-179 dipole moments, 2173-174 Transalkylation reactions homolytic cleavage reactions, 2187 cobalt to mercury, 1k421 hydrogenolysis, 2182 cobalt to palladium, 1k424-425 magnetic properties, 2173 cobalt to thallium, 11:424 olefin elimination, 2186 Transamination reactions, organoboron physical properties, 2168-177 compounds, 10244 preparation, 2158-167 Transannular addition, 238, 45 reactions, 2178-204 Transannular cyclization solvolysis, 2179 of coordinated silylcyclooctatetraenes, spectral properties, 7:168-173 15134 Transition metal allenyl complexes in formation of pentalene complexes, ligand dynamics, 32100-107 15135-136 NMR characteristics, 3293-100 Transannular effects, in ferrocenes, 1040 reactivity, 32107-124 (tvuns-1,3-dimethylindane)Cr(CO)~,M288 structure, 3252-95 Transition metal allenyl complexes 318

synthesis, 3242-83 structure, 332 Transition metal-based polymers, by ring- X-ray diffraction, 33:4 opening polymerization, 32131-165 homonuclear tetrametal units Transition metal carbonyls, 38163-164 deprotonation, 3319, 21, 28 Transition metal carbyne complexes, electrochemistry, 33:25 2251 -1 11 electrophiles, reactions with, 3322 bonding, 22.52-53 geometrical parameters, 33:20 as reaction intermediates, 27:100-101 homometallic boride, 3322 reactions, 27:69-103 NMR data, 3318-19,22,28 with acetylenes, 2289-94 phosphine ligands, 33:22-23, 25 acid-induced coupling, 2283-84 restrictions, 33:18 with acids, 2278-81 tetracobalt-based, 3330-32 alkyne metathesis, 2R90 tetrairon-based, 3318-27 with chalcogenides, 2294-95 tetranickel-based, 33:32 cleavage of carbyne, 27:97-98 tetraruthenium-based, 33:20, 27-30 coupling of carbyne ligands, 27:83-85 X-ray data, 3318, 23, 27-28 with electrophiles, 2278-82 homonuclear trimetal units formation of ketenyl compounds, B-C bond distances, 33:13 27:75-77 cluster expansion reactions, 339-10 with Lewis acids, 2281-82 deprotonation, 338-9 with metal complexes, 2285-89 electronic structure, 337, 10 nucleophilic addition, 27:70-72 clectrophiles, reactivity with, 3312 nucleophilic substitution, 2272-75 Fe3, core, 336,8 photochemical reactions, 2298 Fenske-Hall calculations, 337, 10 polymerization, 27:94 geometry, 335, 18 reductive coupling, 2R83 NMR data, 337-8. 10, 13 substitution of carbyne, 2295 Osl core, 33:lO-11 transformation to vinylidenes, 2295-97 (RO)X2B L, adducts of, 335 structure, 2253-55 structure, 335, 7, 10, 13, 16 synthesis, 2756-69 tricobalt-based, 335, 16-18 Transition metal clusters triiron-based, 33:6-10, 15-16 alkync couplings, 33117-118 triosmium-based, 338-15 allylalcohol conversion, mechanism, triruthenium-based, 335, 9, 14-15 35112 interstitial boron atoms, 33:34-36 anionic carbonyls of nickel, reaction with mixed metal aromatic halides, 12232 cobalt-iron, 3333 arene benzylation, 35115 gold-iron, 3333 aromatic bond activation, 35114-115 gold-ruthenium, 3333 arsenic clusters, catalytic reactions involv- ruthenium-iron, 3333-34 ing CO and H2,3581 carbon-carbon coupling, 35112-118 auraferraboranes. 3322-25 carbon-nitrogen coupling, 35118-12 1 boron atoms in as catalysts for ethylene glycol synthesis homonuclear dimetal units mixed metal systems, 1282-83 B,H6 group, coordination mode, 332 mixed metal systems, 1282-83 dicobalt-based, 334-5 rhodium, 17:80-83 diiron-based, 333 catalytic applications, 3542-43 dimanganese-based, 333-4 catalytic reactions with CO, 3544-49 ditantalum-based, 33:2 carbonylation of ferraborane, preparation of, 333 alcohols, 3344-45 NMR data, 33:2-4 amines, 35:45-46 319 Transition metal allenyl complexes

heterocycles, 3546 dicobaltaboranes, 334-5 deoxygenation of Diels-Alder cycloaddition, 35110 nitro compounds, 35:48-49 diene cyclodimerization, 35113-114 oximes, 3546-48 diene isomerization, 35108 catalytic reactions with CO and Hz, effect of formation during hydroformyla- 3574-95 tion, 1756 homologation reactions, 3590-92 electrochemistry, 3325-26 hydroformylation of olefins, 3581-85 enantioselective isornerization, 33111 hydroformylation reactions, 3580-89 FeZBzcore, 333 hydrogenation of carbon monoxide, Fe3B core, 336-8 3576-79 ferraborane, 333 miscellaneous, 3593-95 gold clusters syngas reactions, 3574-80 catalytic reactions with CO and H2, catalytic reactions with CO and H20, 3591 3595-107 isomerization and rearrangement reac- hydroformylation using water, tions, 35108 3599-102 homogeneous vs. heterogeneous catalysis, hydrogenation using water, 35102-104 3542-43 hydrogen formation, 3598 iridium clusters hydrohydroxymehthylation, 35100-101 catalytic reactions with miscellaneous, 35104-107 Co and H20,35101,103 nitrobenzene reduction, 35103 HZ, 3551 water-gas shift reaction, 3595-99 isomerization and rearrangement reac- catalytic reactions with HZ,3549-73 tions, 35120 alkenes to alkanes, 3550-53 iron clusters hydrogenation of catalytic reactions with acetylenes, 3560-64 co, 35:45 alkynes, 3561-63 CO and HZ,3582-83,87,90-91, 93 carbonyl, 3564-66 CO and H20,3397-99,101-102, nitrogen containing functions, 105 3567-68 H2, 3549, 61-63, 67-68,73 olefins, 3549-60 isomerization and rearangement reac- hydrogen transfer reactions, 3567, tions, 35108-109, 113-114. 121 69-72 isomerization, 35:107-112 catalytic reactions with silanes, 3572-73 miscellaneous, 35121-122 catalytic turnover, 35:43-44 molybdenum clusters cobalt clusters catalytic reactions with catalytic reactions with CO and H2. 3581 CO, 3546 Hz, 3553, 73 CO and H2, 3576,78-79, 81-85, 88- isomerization and rearrangement reac- 92. 95 tions, 35121 CO and H20,35101, 103-104 nickelaboranes, 33:32 H2,3551-52,62,65,73 nickel clusters isomerization and rearrangement reac- catalytic reactions with H2, 3551-53, tions, 35108-109,113-114,117 62-63,68 Co3B core, 33:16-18 isomerization and rearrangment reac- copper clusters, catalytic reactions with tions, 35113 CO and H2, 3578 nickel isocyanides in acetylene hydrogena- cross aldol-type, 35116-117 tion, 17:235 definition, 3541-42 olefin isomerization, 35108, 110 Transition metal allenyl complexes 320

catalytic cycle, 35109 hydride bridge, 2680 Os3B core, 3310-14, 16-17 in unbridged clusters, 2679 osmium clusters Transition metal complexes catalytic reactions with acyclic pentadienyl, see Acyclic pentadie- CO and H20,3997,100, 103 nylmetal complexes, of transition Hz, 3550-53,59-60,62,64,67-68 metals isomerization and rearrangement reac- alkoxycarbonyl, 28:155-157 tions, 35109-110, 115, 120-121 alkyl halide, 38:62 palladium clusters n-allyl, 371-91 catalytic reactions with H2,3553 allylic bond cleavage, oxidative addition, isomerization and rearrangement reac- 34113-123 tions, 35108, 121 allylic oxygen bond cleavage platinum clusters insertion-@-elimination,34126-128 catalytic reactions with olefinic insertion, 34:128-129 CO and HZ,3578, 82 a-ally1 complexes CO and HzO. 35103 alcohol cleavage, M121-123 HZ, 3555, 63, 70 carbonate cleavage, 34118-119 isomerization and rearrangement reac- carboxylate cleavage, N114- 117 tions, 35114 catalyst precursors, 34113 rearrangement, 35112 catalytic process, M113-114 rhenium clusters catalytic reactions with ether cleavage, 34:llY-121 CO and H2, 3578, 92 nucleophilic substitution, mechanism, rhodium clusters, catalytic reactions with 34114 co, 3544-45 n-ally1 palladium complexes, CO and H,, 3575,78,81-89,92,94-95 34113-114 CO and HzO, 3598, 100-107 processes, types of, 34112-113 Hz, 3551, 55-57,61, 64-67,73 &2’, 34124-126 ruthenium clusters without n-ally1 complexes catalytic reactions with alkenyl carboxylate cleavage, co, 3544-49 34:128-129 CO and H2, 3.575-84,86-93,95 carbonate cleavage, 34124-126 CO and HIO, 3596-101,103-107 ether cleavage, 34:126-128 HZ,3549-55,58-62,65, 68-73 arene, 37:292 isomerization and rearrangement reac- bimetallic and trimetallic, 3R219-310 tions, 35108-113, 116-122 carbamoyl, 28155-1 57 tetracobaltaboranes, 33:30-32 carbonyl, photochemistry, 26:297-375 tctraferraboranes, 3318-23 chromium tetraruthenaboranes, 33:27-28 [Cr(H20), CH2XIZ+,33243 triruthenium-based, 33: 14- 15 [q-C,H4Me)Cr(NO),CL], 33242 tungsten clusters, catalytic reactions with [ q-C5R5)Cr(NO2CH2X],33242-243 HZ, 3553 cobalt Transition metal clusters, triosmium, [Co(C0)4CHzCI],33249 2670-80 as doubly bridging ligands, 2673-78 33249-250 interatomic distances, &74 [CP*CO(CO)(CI), 33249-250 naked metal atom bridges. 26:75 [CPCO(PMe3) (X)CH*XJ , 33248 as terminal bridging ligands, 2671-73 halomethyl cobaloximes, 33251 in tetrahedral clusters, 2679-80 porphyrins, 33251 as triply bridging ligands. 2678-81 cyclobutadiene, 4:95- 141 carbonyl bridge, 2680 cyclopentadien yl, 26125-1 26 321 Transition metal complexes

disilene, 39268-269 halogenomethyl complexes, 33266 electron-transfer reactions, 231-93 [Pt(cod)(CH,)CH,CI], 33269 mediation by CO Iigands, 23292-296 [Pt( dppm)( CH2C1)2],33269 fluxional and nonrigid behavior of a-de- [pt(pph2(2-C,H,CH,))(PPh,)LlBF,, rivatives, 16211-239 33264 gold [Pt(PPh3)2( Cl)CH2CI], 33:261-262 [(A~(CHZ)~PPH~J*(B~)CH~CII, [Pt(PPh,),(I)CHzI], 33262 33271-272 [Pt( PPh,)I( CHzPPh3)2]1, 33268 [{AU(CH~)~PPH~]Z(I)CH,C~],33272 [Pt(tdpea)CH,Cl]+, 33265 [Au(L)CH~CI],33271 propargyl, 324.5-48 hydroxycarbonyl, 28:155-159 reactions with carbenes, 9422 infrared studies of carbonyl radical redistribution reactions, 6256-262, anions, 15311-312 239.5-129 iridium, [Ir(PPh,),(CO)CH,Cl], 33257 acetylacetonates, 6260 iron alkyls and aryls, 6256 [CpFe(C02)CH2CI], 33236-237 carbonyls, 6260 [F~(P(~CHM~,),),(CO~)(I)CHZII, a-complexes, 6:261 33~240-241 rhenium synthesis, 33:236-240 [LRe(CO)(NO)CH21]BF4, 33247-248 triphenylphosphine containing, 33239 [Re(P(OPh)&-(CO)3CH2XJ, 33:247 Lewis base-carbonyl, 3181-252 rhodium manganese [Cp*Rh(CO)(I)CH21], 33255 [Mn(C0)&H2X], 33247 [CpRh( L)2CH2I]PF6,3325 1 [Mn(PPh,)( CO),CH2X], 33:247 [CpRh( L)(L)CHzI]PFb, 33:251 mass spectra of organometallic deriva- [CpRh(Pme3)2CHZCl]PF6,33252 tives, 6:273-323 [CpRh(PMe3)(v-CHzSe)], 33:255 7-membered carbocyclic hydrocarbons, [CpRh( P( OMe),J( I)CH21], 33253 4354-368 halomethyls, 33:259 8-membered carbocyclic hydrocarbons, iodomethyls, 33:258 4369-384 macrocyclic halogenomethyls, molecular rearrangement of clusters, 33~256-257 16319-346 [Rh(drnpe),( C1)CH2Cl]-Cl CH2Cl,, molybdenum 33:256-257 [CpMo(CO)?CH2X], 33244 ruthenium, [C~RU(CO)~CH,CI],33240 pentamethylcyclopentadienyl analogs, silene, 3985-89 33245 tungsten a-olefin, 3:47-71 [Cp W( CO),CH2X], 33245-246 of organosilyl-substituted a-ligands, pentamethylcyclopentadienyl analogs, 15113-139 33246 organotin derivatives, 982 unsaturated molecules, 1433-61 nature of tin-metal bond, 983 Transition metal complexes, C-0 bond acti- osmium, [OS(PP~,),(CO)~(I)CH~I], vation by 33241 allylic oxygen bond cleavage palladium non Ir-ally1 complexes, 34124-129 ~is-[Pd(PPh?)2(I)CH21],33259 a-ally1 complexes, 3k113-123 halogenomethyl complexes, 33260 C-0 cleavage platinum concerted processes, 34:129-139 cationic metallocycles, 33264 two-step mechanisms, 34139-140 cis-[Pt (PPh, )2( CL) CH2PPh31 +, C = 0 cleavage 33262-263 aldehydes, 34:140-143 Transition metal complexes 322

esters, 34:140-143 anionic, 221-50 ketones, 34140-143 as catalysts, 2244-46 Transition metal complexes, C - 0 single interaction with sodium ions, 2224 bond cleavage ion pairing, 2223-27 concerted processes reactions, 27:28-43 acid anhydrides, 34.134-136 with acid halides, aldehydes, and ke- alcohols, 34138-139 tones, 2241-43 cyclic ethers, 34136-138 with alkyl halides, 2235-41 esters, 34130-134 with Bransted acids, 2233-34 two-step mechanisms, 34139-140 with electrophiles, 2230-34 Transition metal complexes, trifluoro- with Lewis acids, 2230-33 methyl-containing scope, 2728-30 chemistry, 33218-234 spectroscopic properties, 224-8, 20-27 Group 3-5 metals, derivatives, 35218 structural characteristics, 229-20 Group 6 metals, derivatives, binuclear, see Binuclear transition metal 35218-221 hydrides Group 7 metals, derivatives, manganesepentacarbonyl alkyl reaction, 35221-223 37:183-184 Group 8 metals, derivatives, rheniumpentacarbonyl alkyl reaction, 35223-227 37206 Group 9 metals, derivatives, Transition metal n-complexes, nonrigidity 35227-229 in, 16211-239 Group 10 metals, derivatives, allyls, 16:228-230 35230-231 effect of [NO]+ vs. CO, 16228-229 Group 11 metals, derivatives, coupling of n-ligand rotation and CO re- 35231-232 arrangement, 16931-236 Group 12 metals, derivatives, iron complexes, 16:231 35233-234 NMR studies, 16211-222 early studies, 35212-218 analysis of kinetic data, 16212 backbonding, 35213 computer-simulated spectra, 16:212 CF?I, 35212-215 line shapes, 16215 d block elements, 35912-213 olefin rotation, 16225-228 formation, 35213-215 polyene metal tricarbonyls, 16:234-236 preparation, 35214-217 carbonyl scrambling, 16234 properties, 35213 or iron, 16234-236 reactions, 35214 ring whizzers, 16:222-224 reagents, 35226-217 cycloheptadienyl, 16223-224 u-bonding manifold, 35213 cyclooctatetraenes, 16:223-224 thermal decarbonylation method, cyclopentadienyls, 16223-234 35213-214 1,2-shifts, 16:222-224 prospects, 35235-236 rotation of n-ligands, 16225-231 scope, 35211-212 allyls, 16228-230 structural data synopsis, 35234-235 olefins, 16:225-228 Transition metal halides Transition metal reactivity, computer pro- homogeneous catalysis, 38167-171 gram, 26165-216 reaction with fluorocarbon Grignard re- bonding representations, W169 agents, 1:184-186 catalyst representation, 26168-169 with fluorocarbon lithium reagents, complexes recognized, 26:172 1~184-186 for coordination chemistry, 26:175-191 Transition metal hydrides electronic representation, 26169-172 323 Triazenes

flow chart, 26167 via bridging methyl, 20332-333 geometries recognzed, 26:172 electrophilic transmethylation, intermolecular reactions, 261 91-195 20333-336 ligand representation, a171 free radical transmethylation, limitations, 26:168 20336-337 reaction representation, 26:172-174 heterolytic M-C cleavage, 20332 steps, 26167-168 homolytic M-C cleavage, 20332 stereospecificity, 26210 nucleophilic transmethylation, structural representations, 26169-172 20338-340 substructure representation, 26173 and standard reduction potentials, Transition metals 20334-335 bonding of X-Y u fragment, B300-301 of mercuric acetate, 20317 bonds with arsenic, 4199 by methylcobalamin, 20316-321 I3C chemical shifts of carbonyl deriva- by methylmetals, 20322-323 tives, U.144-145, 172-176 by methylsulfonium salts, 20:322 chemistry Transuranium elements, organo derivatives, boron heterocycles, 18:301-340 9389-391 optically active complexes, 18151-206 cyclooctatetraene complexes, 9390 elimination of sulfur dioxide from sulfi- cyclopentadienyls, 9389 nates, l236-37 Triacylrhenato complexes, 25:55-56 heteronuclear multiple bonding, 3947-62 Trialkylamine boranes, hydroboration with insertion of sulfur dioxide into carbon dienes, 2276-278 bonded compounds, 1231-79 hydroboration with polyolefins, mixed alkali metal compounds, 27:208- 2278-279 216,246-251 Trialkylboranes, 39367 mixed-metal clusters with carbollylger- displacement, 2280-282 manium, 26266-267 synthesis, 2277 organic and hydride chemistry, 12:l-27 Trialkylcalconium ions, 3872 a-bonded organometallic compounds, Trialkylgallium, 3869 347-156 Trialkylindium, 38:69 reactivity, computers and, 26A65-216 Tnalkylphosphonium dithiocarboxylate a-bonded organometallic compounds, complexes, synthesis, 28:235-236 34-47 Triamines, multiple bonding, 3918-26 terphenyl derivatives, M14-17 Triarylboranes, 39367 d-d Transitions, in organocobalt complexes, Triarylborirene, 39362 11:350 Triarylphosphinegold complexes, 32247 Transition state, in substitution reactions of 1,2,4-Triaza-3,5-diborolidine,18322-323 metal ncomplexes, 10348 1,3,5-Triaza-7-phosphaadamantane,38:179 five-coordinate, 10349 Triazenes, derivatives of Group IV ele- importance of coordination number, ments, M180-202 10349,351 cis-trans isomerization, M194-195 Transmetallation, in pentadienyllithium hindered rotation, 24197-198 complexes, 26133-134 1,3-migration, 24195-197 Transmetallation reactions 'H NMR spectra, 24:191, 193 perfluorovinyl-lithium, k148-149 physical properties, 24988-190 silicon-transition metal complexes, 11:278 radical reactions, 24:193-194 with thallium, 1M69 substitution reactions, %A89 Transmethylation, see also Biomethylation with metal carbonyl halides, 24189, effect of solution salinity, 20323-324 192 mechanism, 20332-340 synthesis, 24:180-188,190,192 Triazenes 324

from amides and diazonium salts, molybdenum, reaction with dienes, 24:185-186 26338-339 via cycloaddition reactions, at85 Tricarbonyl-$-cyclopentadienylmethyl- from metal triazenides, 24187 molybdenum, reaction with 1,3-dienes, nitrogen chain building, 24:185-186 26336-338 nitrogen chain cleavage, M186 Tricarbonyl-q4-dienebis(q5-methylcyclo- reduction of azides, 24180-185 pentadieny1)dimolybdenum complexes via substituent exchange, 24187-188 stereochemistry, 26349 thermolysis, 24:198-202 structure, 26349-350 acyclic derivatives, M198-200 synthesis, 26347 cyclic derivatives, 24:201-202 Tricarbonyl(diglyme)molybdenum, 26331 to radicals, 24198-200 Tricarbonyl-qh-8.8-dimethylheptafulvene- Triazide(phenyl)silane, flash pyrolysis, chromium 39189 cycloaddition reactions with dienes, Triazidophenylsilane, 39189 26327-329 Triazolines, thermolysis, 24201-202 reactions with pentafulvenes, 26334 Tribenzylboranes, 39:369 Tricarbonyl-~2~5-",'2-1l-isopropylidene- 1,3,3-Tribrom0-2-rert-butyl-2,2- bicyclo [4.4.1]undeca-2,4,8- dimethyldisilane, 3R14 trienechromium, 26:332 1-(2,4,6-Tri-t-butylphenyl)-2,2- Tricarbonyl[ 'J.l"-(13-isopropylidene- tricycl0[6.2.2.1~~~]trideca-3.5.9- dimesitylgermaphosphene, 39:303-304 Tri-~-butylsilylazide,39166, 176 triene)]chromium, 26329 Tricarbonyl-qh-mesitylemolybdenum,reac- Tri-t-butylsilylsodium, 39:163 tion with dienes, 26299 Tri-tert-butylsilylsodium anion, 3813-14 Tricarbonylmetallate(3-) anion of cobalt Tri(t-butyl)tin chloride, 38192 characterization Tricarbonyl-q4:*~bicyclo[4.4.]undeca-2,4,8- IR spectrum, 3k33-34 trienechromium complexes purification of trisodium salt, 3k33 ligand cleavage, 26330 germanium, tin, and lead derivative, synthesis, 26326 31:34-35 Tricarbonylchromium $-arene n-com- hydride derivative, 3k35 plexes, third-order nonlinear optics, isocyanide derivative, 31:35-36 43375-376 synthesis Tricarbonyl(pL-q"-1,3-cycloheptadien-l- reduction tetracarbonyl(1-) anion, yl)hydridobis( vS-methylcyclopenta- 31:31-33 dienyl)dimolybdenum, 26350 tripotassium salt, 3k32-34 Tricarbonyl-q6~1,3,5-cycloheptatriene- trisodium salt, 31:32 chromium Tricarbonylrnetallate(3-) anion of rhodium cycloaddition reactions with dienes, and iridium, 3k36-39 26325-327 characterization, 3k37 reaction with pentafulvenes, 26333-334 germanium and tin derivative, 3k38 Tricarbonyl-q6-l,3,5-cycloheptatriene- protonation, 3k37-38 chromium complexes, reactions with synthesis, 31:36-37 conjugated dienes, 26325-335 Tri~arbonyl-$:"~-2-methyl-(E)-3-[3(8),6-m- Tricarbonyl-q6~l,3,5-cycloheptatriene- menthoadiene-6-yl]-2-butene-l- molybdenum. 26331 ylmanganes. 26364-365 Tricarbonyl-q6~l.3,5,7-cyclooc-tatetraene- Tri~arbonyl-ql-~6.7-l ,3,5,5,7- chromium, reaction with pentafulvenes, pentamethylcyclononadiene-l- 26334-335 ylmanganes, 26:356-357 Tricarbonyl[2-( ~5-cyclopentadienyl)ethyl]- Tricarbonyl-qh~toluenechrornium,26316 325 Trimethylsilanolate

Tricarbonyl-~4~tricyclo[6.3.0.02~7]undeca-3,5-Triisopropylphenyl species, synthesis, 445 dienetrimethylphosphitetungsten Triisopropylphosphine, 32244 ligand conformation, 26305 Trimesitylaziodsilane, 39160 structure, 26302 1,2,2-Trimestyl-2-phenyldiborane(4),39373 Tricarbonyltungsten(6-) anion Trimetallic complexes IR spectral evidence, 3k46 u-alkyl complexes, 37:235, 244, 246, 253. speculative preparation, 3k45-46 265 Trichlorogermane, 37:18, 26, 29 m-benzene complexes, 32298-300 Trichlorohydrosilane, 383 u-carbene complexes, 32269, 272-273 Trichlorosilane, 37:23, 3821 s-cyclopentadienyl complexes, 37:276- Trichlorosilyl anion, 3821, 44 277, 286-287 Trichlorosilyllithium, 3820-21 Trimethylaluminum Trichylohexylphosphonium dithioformate bonding, 1330 complexes, 7'- or $-bonded, preparation, 38:69 28247-249 Trimethylamine oxide Tricobaltcarbon decacarbonyl cation, decarbonylations of, a184 14110-119 use in substitution chemistry of carbonyl electrophilic nature, 14115 clusters, 18232 mechanism of formation, 14116-119 Trimethylamine-trimethylborane exchange, reactions 8:201 acylation, 14111-119 1,3,5-Trimethyl-1,4-cyclohexadiene,29:191 with alkyltin compounds, 14115-116 Trimethylene manganese carbonyl, 326 with triethylsilane, 14116 Trimethylenemethane, 3989 synthesis cycloaddition to alkenes, 22300-304 via aluminum chloride, 14:115 from (C0)9C03CC02R,14111-112 7r-Trimethylenemethane complexes, 1054 of hexafluorophosphate salt, 14112 Trimethylenemethane metal complexes, Tricobaltnonacarbonyl complexes, 22279-309 u345-347 reactions, 22294-300 Tricyanomethanide complexes, 2230 with electrophiles, 27:294-295 Tricycl0[2.2.0.0~~~]hexasilane,3211 modification reactions, 27:299-300 Tricyclophosphahexane, synthesis with phos- with nucleophiles, 22295-297 phaalkynes, 4k50 redox reactions, 22298 Tridecacarbonyl-p-7' ' (E)-3-methyl-1,3- with tertiary phosphines, 22297-298 butadiene-1-yltrirhenium, 26369 role in organic synthesis, 22300-307 Triene structure and bonding, 22289-294 iron carbonyl complexes, k20-22 synthesis, 22279-289 rhodium complexes, 26153 from allyl silanes, 22285-287 3-Triethylsilyoxypentadienyllithium,26133 by dehalogenation, 22280-282 Trifluoroacetato ruthenium(I1) complexes, miscellaneous methods, 22287-289 29172 by ring opening of alkylidenecyclopro- Trifluoromethanesulfonic acid, intercalation panes, 22283-285 of, 28129 by thermal extrusion, 27:282-283 Trifluoromethyl, transition metal complexes Trimethylpentadienyltin, 26149 containing, 35218-234 Trimethylphosphine benzene derivative, N-Trifluoromethylgermanimine, 39290 29175 Trigermenyl allyl anion, in digermene syn- Trimethylplatinum iodide, 32170 thesis, 44:132 1,2,3-Trimethylsilane, dehydrocoupling for Trigermirane, photolysis, 44A29-130 polymerization, 42382 Trihalogenosilanes, synthesis, 3214 Trimethylsilanolate, 3978 Trimethylsiloxy group 326

Trimethylsiloxy group, pharmacology, by number of metal-metal bonds, 18282-283 264-6 Trimethylsilylazide, reaction with electron counting, 263-6 germylenes, a146 with four 0s-0s bonds, 2638-39 N-Trimethylsilylbenzophenoneimine, with Group IV elements, 26:68-70 39123, 128, 149 nuclearity, changes of, 26:65-68 Trimethylsilylethynyl complexes, 38101, decrease, 2665-66 116-117 increase, 26:66-68 Trimethylsilylmethyl group (MelSiCH2) by reduction of dodecacarbonyltios- trans influence, 1k317 mium, 2666 transition metal complexes, 1k310-323 by strongly bridging ligands, 26:67 reactions, 11:321-323 by vacuum thermolysis, 26:67 synthesis, 1k318-321 with one 0s-0s bond, 266-7 Trimethylsilyl mixed alkali metal com- 0s-0s bond lengths, 265 pounds, 27221-224 physical properties, 2k2-3 Trimethylsilylstannacarboranes, 26277 reactions with diphenylacetylene, Trimethyltin, halides, 1468-71 2661-63 fluoride, 1468-69 structural types, 266-39 structural studies, 1468-69 with three 0s-0s bonds, unbridged, 2613 molecular complexes, 1477-83 with three 0s-0s bonds with doubly spectral studies, 1468-71 bridging ligands, 2613-23 Trimethyltin compounds, 5146-148, alkylidyne bridging ligands, 2621 -22 151-156 bridged 0s-0s distances, %20 Trimethysilyl anion, 38:13-14 chirality, 2622 Trinuclear carbonyl clusters, molecular re- diastereomers, 2622-23 arrangements, 16326-329 with double-atom bridge, N16 of iron, 16326 bridged 0s-0s bond length, 2616, 20 mechanism, 16326 bridging ligands, 2616 mixed metal species, 16326 geometry, XI9 of osmium, 16328 hydride location, Z16 of ruthenium, 1k328 nonbridged 0s-0s distance, 2619-20 Triorgano (N-phenylformamido) tins, other metal substituents, %16 38205 synthesis, 2616 Triorganostibine sulfides, 14192-197 formation nature of Sb-S bond, 14:193-194 from insertion reactions, 26:13, 18 n-bonding, 14194 by nucleophilic attack, 2618-19 spectral studies, 14193-194 by oxidative addition, 2618 reactions, 14195-197 geometry, 2619 Triorganotin hydrides, 38205 nonbridged 0s-0s distance, 2619-20 Triosmium clusters, 261-96 phosphine-substituted compounds, bonding orbitals, 265 2621 bridging ligand mobility, 2658-61 with single-atom bridge, 2614-15 bridging ligands, 268-38 bridged 0s-0s distance, 2614-15,20 with bridging transition metal atoms, bridging atoms, 2614-15 2670-81 geometry, 2619 as catalysts, 26:63-65 hydride location, 2694-15 chemisorbed species, 263 nonbridged 0s-0s distance, 2620 chemistry of hydrocarbon ligands, other metal substituents, 2614-15 2655-65 synthesis, 2614-15 classification. 264-39 with triple-atom bridge, 2617 Tripodal rotation

bridged 0s-0s distance, 2617, 20 SR clusters, %:lo, 12-13 bridging atoms, 2617 high-temperature reactions, 2612 geometry, 2619 hydrogenation, 2612 nonbridged 0s-0s distance, 2620 with three-electron donor ligands, other metal substituents, 2617 2610 synthesis, 2617 types of systems, 26:4-39 vinyl ligands, 2620-21 Triosmium dodecacarbonyl, see Dodecacar- with three 0s-0s bonds with triply bridg- bonyltriosmium ing ligands, 2623-38 Triphenylarsine, structure, 4199 five-electron donors, 2632-37 Triphenylbenzene, nitration, 44:39-40 cyclic organic systems, 2635 Triphenylborane, 39382 hydrocarbon bridges, 26:34 Triphenylborirene, preparation, 39377-378 phenolic systems, 26:36-37 Triphenylcarbenium tetrafluoroborate, tertiary phosphine systems, 2635 methyl rheniumpentacarbonyl reaction, four-electron donor ligands, 2625-32 37:208 p3-alkyne compounds, 2628-29 Triphenylchlorosilane, 383-4 aniline derivatives, 2632-33 Triphenylcyclopentadiene, synthesis of, benzyne clusters, 2630 33:303 hydride migration, 2627 Triphenylmethylsodium TMEDA complex, ketenylidene ligands, 2627 26:224 octahedral environment, 2626 Triphenylphosphine phenol derivatives, 2632-33 rheniumpentacarbonyl alkyl reaction, ortho-phenylene complexes, 2631 32211 synthesis, 2627 sulfonation, 38164 vibrational analysis, 2626 Triphenylphosphine complexes, see Phos- vinylidene ligands, 2627-28 phine complexes zwitterions, 2630-31 Triphenylsilylhydrazine, synthesis, 40.3 seven-electron donors, 2638 Tnphosphides, multiple bonding, 3926-27, six-electron donors, 2636-38 37 benzene ligands, 26:38 Triple-decker sandwich complexes, 18:306- three-electron donor ligands, 2624-25 307,325-333 p3-alkylidyne complexes, 2624 bonding, 18306-307 hydride positions, 2624 containing ChB3ring systems, 18329-330 interatomic distances, 26:24 cyclooctatetraene with two linear 0s-0s bonds, 267-8 cobalt cyclopentadienyl, 18328 bonding angles, 26:s titanium, 18328 with two 0s-0s bonds, terminal atoms cyclopentadienyl nickel, 18306-307, 325, bridged, 262-13 328 p3-allenylidene complex, 2612 1,3-diborolenes, 18306-307, 330-332 bridged 0sdistances, 269-13 1,2,5-thiadiborolenes, 18326-327, bridging modes, 269 332-333 p3-capping ligands, 26.12-13 Tripodal orientation, (arene)Cr(C0)3 com- decarbonylation, 269, 12 plexes diacyl compounds, 2611 electrophilic attack, 34293 with doubly and triply bridging ligands, nucleophilic attack, 34294 2611-12 Tripodal rotation formation, 269 arene complexes, localized double bonds with four-electron donor ligands, 26:13 in, 34311-312 generation of acyl ligands, 26:lO-11 benzyl chromium tricarbonyl cations with ketene bridge, 269 deshielding, 34:315 Tripodal rotation 328

extended Hiickel molecular orbital ap- reactions, a351-352 proach, 34312-315 benzene formation, 12:351-352 minimum energy structure, 34313-314 structure, Kk349-351 NMR spectra, 34313-314 Trisarsenides, multiple bonding, 39:26-38 rotational barriers, 34314-315 Trisaryloxides, 3939 [(ben~yl)Cr(CO)~]',34296 Tris(~arbonyl)-~~-trimethylenemethaneiron (1,3,5-~yclohexatriene)Cr(CO)~,34295 reactions cyclopentadienyl complexes, 34319-321 with electrophiles, 27294 different eclipsed isomer conversion, with tertiary phosphines, 27297-298 34290 role in organic synthesis, 27:301 electronic barriers, 3431 1-319 structure, 27289-290 fulvene complexes Tris(3,5-dimethylpyrazolyl)borate ligand, EHMO calculations, 34318 39:59 NMR spectra, 34316-318 Tris(dimethylsily1) silyllithium, 38:28 X-ray crystallography, 34316 Trisilane, 39232-236, 254 (HEB)Cr(CO)*CS, 34300-301,303 silyene-Lewis base complex synthesis, (HEB)Cr(CO),L complexes 4324-25.39 (ChEth)Mconformers, M300 Trisilylamines, 9316-318 chemical shift difference, 34300 bis(triorganosily1)amide anions, NMR spectra, 34301 9~318-321 proximal-disial arrangement, 34:299- isosteres of ylid series, 9:328 300,303 Tris(p-tolyl)arsine, structure, 4200 X-ray crystallography, 34301 Tris(p-xylyl)arsine, structure, 4200 (HEB)Cr(CO)I,'L" complexes, 34:306, Trispyrazolylborate complexes, 3959, 61 310 Tris(supersilyl)cyclotrisilane, 3%34 NMR spectra, 34309 Tristannanes, 38:205-211 proximal-distal environments, 34306, Tris(tetrahydrofuran)magesium-s-czs-l,4- 308 diphenylbutadiene, 26233, 236 X-ray crystallography, 34307-308 Tris(trimethyl)phenylsilane, silyene-Lewis (HEB)Cr(C0)?PR3, a301-303 base complex synthesis, 43:27 (hexaethylbenzene)Cr(CO)3, 34297-299 Tris(trimethylsilyl)cyclopentadiene, synthe- kinetic, 34289-293 sis of, 33304-305 NMR studies, M291 Tris( trimethylsilyl)cyclopentadienylindium, (pentaethylacetophenone)Cr( CO)? 33341 alkyl rotation, 34306 Tris( trimethylsilyl)cyclopentadienyllithium, NMR spectra, 34304-305 26221, 33339-340 proximal-distal arrangement, 34304 quinuclidine adduct, 26:221 X-ray crystal structure, 34304 TMEDA adduct, 26:225 relaxation time structure, M319 Tris(trimethy1silyl)cyclopentadienylmagnes- solid-state NMR measurements, 34319 ium complexes, 26233-234 sterically hindered arenes, 34310-31 1 Tris(trimethylsilyl)cyclopentadienyl(methyl)- steric barriers, 34297-31 1 magnesium, TMEDA adduct, 26233 symmetry equivalent isomer conversion, Tris(trimethylsilyl)cyclopentadienylthal- 34289-290 lium, 33341 thermodynamically restricted, 34289-293 Tris(trimethylsilyl)silyllilthium, 3828 Triruthenium carbonyls, water-gas shift ca- Trisulfonated triphenylphosphine, see talysis of, 28192 TPPTS Trisalkynedicobalttetracarbonyl complexes, Tri(tert-butyl)cyclopentadiene, synthesis of, 12348-352 33305-306 preparation, 12348-349 [3]Trithiaferrocenophanes, atom abstrac- 329 Tungsten

tion-induced polymerization, 32160- theoretical studies, 22360-362 162, 164 dinuclear alkyl and aryl complexes Trityl azide, reaction with silylene, 39166 reactions, 22348-353 Trivinylborane, 39362, 384 structure, 22348 Tropone, iron tricarbonyl complexes, k7-8, synthesis, 27:345 42-43, 4363 dinuclear alkyne complexes Tropylium cation, vibrational spectrum, reactions, 22340-344 k302-303 synthesis and structure, 22337-339 Tropylium complexes, 32268 isonitrile adducts, 22362-363 metal, 8137, 148 metallacyclobutadiene complexes, a-Tropylium complexes, 4354-363 27: 3 3 0 - 3 3 2 chromium, 4:356,360-361 reactions, 22333-336 reactions, 4356-357 stability, 22331-332 cobalt, 4359 structure, 22333-334 iron, 4358 synthesis, 22330-33 1 binuclear complexes, 4359 mononuclear alkylidene complexes manganese, 4:362 reactions, 22317-320 molybdenum, 4:356 spectroscopic data, 22314 reaction with sodium cyclopentadie- synthesis, 22312-314, 316-317 nide, 4357 mononuclear alkylidyne complexes platinum, 4:362 reactions, 22325-329 valence tautomerism, 43577360 structure, 22323-325 vanadium, 4358, 360 synthesis, 22320-323 Tropyne, transition metal complexes polynuclear alkylidyne complexes structure and spectroscopy, 42185-186 reactions, 22355-358 synthesis and reactivity, 42181-183, 185 structure, 2R353-354 Trouton constant, fluoroalkylboron com- synthesis, 22353, 355 pound, k154 Tungsten, anionic hydride complexes Tungsten as catalyst, 2245-46 binuclear octacarbonyldihydride anion, reactions, 2228-30 186 with aldehydes, 2242 carhonyl derivatives, 3196-213 with alkyl halides, 2235-41 met allacycles, 26:97 - 124 with Bransted acids, 2233-34 mixed alkali metal compounds, with Lewis acids, 2231-33 22247-251 with small electrophiles, 2234 mixed-metal clusters, 18211-212 spectroscopic properties, 224-8, 23-27 organogallium compounds. 39:48, 52 structural characteristics, 2212-13, 17-19 terminal C-C,O-bonded carbonyls Tungsten carbonyl compounds with alumina, 23241 anions containing cyclopentadienyls, with aluminum derivatives, 23238, 240 2191-202 with magnesium ions, 23235-236 dianions, 2182-184 with sodium ions, 23234-235 hydrides, 2200-202 in triosmium clusters, 26:77-78, 80-81 miscellaneous anions, 2188-190 Tungsten alkoxides, 22311-369 monoanions, 2185-187 carbide complexes, 22364 Tungsten, carbonyl diazene complexes carbonyl complexes aryldiazenes, 3482 carhonyl cleavage reaction, 22364 bisdiazenes, 3480-81 molecular orbitals, 22361-362 diazene metathesis, 3493 structure, 22359-360 diazetines, 3489-90 synthesis, 27:359-360 dimetallacycles, M88,90 Tungsten 330

electronic absorption spectra, 3484, 86, 266-269,275,277,282,289-292,298, 88 300-302 NMR studies, M82 binuclear carbonyl hydride, X54 preparation, 3480-81 of boranes, 2k64, 67 uv-vis spectrum, M84-85 carbonylation, 11:121-122 X-ray analysis, 3487-88 with isocyanides, 1149 Tungsten carbonyls, substitution mechanism carbonyl diazirine, 3481,86 mine complexes, 21:127-130 cobalt-alkyne, synthesis, 4175 anionic pentacarbonyl carboxylate, cyanate, 2481 2k138-139 1,4-diaza-l,3-butadienes cis-labilization, 2k138 allyls, 2k160-161, 168, 171-172 CO dissociation rate parameters, 21:117 bonding, 2kl72-175 CO vs. phosphine labilization, 2k121 with chelate ligand, 2k160-161, 168, and cone angles, 2M21 170 effect of hydroxide, 2k138-139 radical anion, 2k217 phenanthroline complexes, 2k143 dicarbonylbis( 7"diene) tetracarbonyl norbornadiene, 2k132-135 dynamic behavior, 26:314-315 I3CO substitution, 21:133 molecular structure, 26:313-314 thiocarbonyl, 21:140 stereochemistry, 26:311-313 Tungsten, carbyne complexes diphenylcarbene pentacarbonyl com- as catalyst, in alkene metathesis, 2290 pound in olefin metathesis, 16:270- reactions 271,299-308 with acetylenes, 2290-94 selectivity, 16305 with acids, 2R78-81 disilene, 39:269 p-ethylene cation, 20241 with aldehydes, 22102 formyls, 206 with carbon monoxide, 2299 p-germylene structure, 20:233 carbyne cleavage, 2297 halides in olefin metathesis, 16:284 carbyne coupling, 2283-85 hexacarbonyl, reactions with conjugated with cyclohexyl isocyanate, 22101-102 dienes, 26:299 with Lewis acids, 2281-82 main group with metal complexes, 2285-89 antimony and bismuth, 31130-137 with methyl cyanate, 22102 gallium, indium, and thallium, 31:92-96 with nucleophiles, 2271-77 germanium, tin, and lead, 31108-113 with other tungsten carbynes, 27:101 tellurium, 3k1.55-157 photolysis, 2298 via metal atom synthesis, 1593 with xylylisocyanide, 2298 p-methyleneoctacarbonyl, 20:186-187, spectroscopic properties, 2256 217 structure, 2254-55 X-ray structure, 20187 synthesis, 27:57-60, 62-69 mixed-metal germanium, 26:264 Tungsten complexes nitrido clusters, 2463, 66, 73 a~etylcarbonyl-~~-cyclopentadienyl-~~- nitrosyl clusters, 24:51 diene, 26341-342 "C NMR spectra alkyl, 38108 of carbenes, 12:143, 171 p-alkylidene, acetylene insertion, 20250 of carbonyl derivatives, 12175, 192 alkylidyne carbaborane, 3153-87 organolithium derivatives alkynyl, 3885, 89, 108, 110, 112-113 binuclear methyl complex, 24397-398 P-T ally1 rearrangement, 16:244-245 bis(cyclopentadienyl)hydride, 24:403, arene, 1363, 65, 69,774'9, 82-84 406 bimetallic, 37:229, 234, 236-237, 242, 250, pentacarbonylcarbene, reaction with nu- 331 Tungsten

cleophilic metal compounds, of dinitrogen, 2311 18231-232 isocyanides, 2310-1 1 phenylethynyl, 38122-123, 134-136 mixed metal clusters, 24111-112 propadienylidenes, 2283-85, 103 sandwich compounds, 2369 reactions, 2287 Tungsten complexes, photochemistry propargyl, 32242 binuclear alkyls, M276 structure, 3283-84 bis(cyclopentadieny1)derivatives reactions of carbonyl anions with carbon chlorotetracarbonylalkylidyne, 24341 dioxide dimethyl, 2276-278 catalyzed methyl formate formation, metallacyclobutanes, 24278-280 22158 methyl hydride, 24287 insertion into metal-methyl bond, dicarbonyl cyclopentadienyliminoacyl, 22148-151 24335 reduction of carbon dioxide, 22154 hexamethyltrimethylphosphine derivative, $-SiH, 30178 24287-288 of substituted cyclopentadienyls, 2k9-12, pentacarbonyl alkylidenes, 24327-329, 36 331-334 vinyl polymerization, 2k11 with alkynes, a333-334 sulfur diimide, 36203 carbonyl substitution, 24329 sulfur dioxide insertion reactions, 1261 with I3CO, M331 tricarbonylcyclopentadienylmethyl,reac- cyclic carbenes, 24329 tions with dienes, 26340-341 diphenyl carbene, 24332-333 122-valence electron, 30:204 electronic spectrum, M327 128-valence electron, 30201-204 energy level diagram, 24328 130-valence electron, 30200-201 vinylidenes, 22:66-68, 88-89, 96, 104- olefin substituted carbenes, 2331-332 105, 110 tricarbonyl cyclopentadienylalkyls, Tungsten complexes, electron-transfer reac. 24280-287 tions Tungsten ~fdienecarbonyls, 26:299 alkyls, 2334 carbonyl scrambling, %307 bridged bimetallics, M100 diene ligand rotation, 26305, 308-310 carbonyl compounds isomerization, %305-307 acyls, 235 ligand exchange, 26311 carbenes, 238 structure, 26:302 carbyne, 239 synthesis, 26300 cyanides, 239 Tungsten halides halides, 2318 in formation of methane from dimethyl- with N-donor ligands, 2312-13 zinc, 12453 or o-quinones, 2317 in olefin metathesis, 12451-489 carbonyl phosphines, 2313-17 metallacyclobutane complex, isomerization, 2315-16 12456-457 cycloheptatrienyl, 2366 Tungsten, isocyanide complexes, cyclopentadienyls 22251-252 alkyls, 2348-49 alkylation, 22295 carbonyls, 23:47 carbonyls, 22:217-218, 225-227 hydrides, 2348 cyclopentadienyls, 22226 nitrosyk, 2349 eight-coordinate cyanides, 22216 diazoalkanes, 2311 homoleptic species, 22221-222 functionalization, 2312 phosphines, 22232 reductive coupling, 2311 Tungsten, pentacarbonyl carbene com- Tungsten 332

plexes, CO exchange processes, W(C0)(3-hexyne)+, synthesis and spec- 12452-453 tral properties, 293 in olefin metathesis, 17:451-453, 459-461, W(CO)(RC-CR),, 294 469,487 W(CO)(RC=CR)LX*, synthesis of, positive charge on carbene carbon, 296-7 12463 W (PhC= CPh),( CO). 295 relative reactivity with olefins, W(RCsCR)Z(S2CNEt2)2, synthesis of, 12463-464 2914-16 ylide formation, 12463 Tungsten(II), halocarbonyl complexes Tungsten(I1) complexes alkylidene complexes alkyne, structures, 2923-24 crystal structures, 4075-76 alkyne ligands, reaction in d4 monomers synthesis, 40:75 alkyne insertion products formation, alkyne complexes 2983-90 crystal structures, &78-79, 81, 87-88 metal-alkyne cleavage reactions, reactions 2990-92 Ag[BF,], 40:85 q2-vinyl ligand formation, 2971-83 anionic donor ligands, &84 bisalkyne bisdithiocarbamate, 2915-16 carbon donor ligands, &79-80 bisalkyne complexes, alkyne rotational l&cyclotetradecadiyne, &85-86 barriers, 2960-61 1,4-diphenyIbutadiyne, 40236 Cp(CO)’W=CR, 293 nitrogen donor ligands, &80-81 CpMo(RC=CR)LX, synthesis, 299-12 oxygen donor ligands, &82,84 CpW(RC=CR)LX syntheses, 299-12 phosphorus donor ligands, 40.81-82 cyclopentadienyl alkyne derivatives, syn- seven-coordinate halocarbonyls, thesis, 299-12 a87 d4 alkyne complexes sulfur donor ligands, 40532, 84 electrochemistry, 2969-71 synthesis, 40:17-78, 87-91 electronic spectra, 2964-68 n-ally1 complexes IR spectra, 2962-64 catalytic activity, &98 internal bisalkyne complexes, 2959 crystal structures, 4092-93, 96-97 internal monoalkyne complexes, reactions with donor ligands 2947-51 arsenic donor ligands, &95 terminal alkyne complexes, 2944-47 bidentate donor ligands, a96 terminal bisalkyne complexes, 2958 carbon donor ligands, 40.94 d4 alkyne monomers, synthesis of, 296-7 nitrogen donor ligands, W95 four-electron alkyne ligands, 291-3 phosphorus donor ligands, 40.95 internal monoalkyne, NMR spectra, synthesis, 40:91-94 2944,41-SO arene complexes mixed alkyne-olefin d4, isolation, 298-9 crystal structure, &lo4 monoalkyne, alkyne rotational barriers, synthesis, 40:103 2951-57 q7-cycloheptatrienyl complexes, &lo4 NMR spectra cyclopentadienyl and related complexes internal bisalkyne complexes, 2957, 59 isomerization, &102-103 terminal bisalkyne complexes, 2957-58 reactions with neutral donor ligands, PhC-Cme, formation from coupling C, &lo2 ligands, 2922-23 synthesis, 40:101-102 pseudotetrahedral derivatives, 293-4 diene complexes terminal alkyne, NMR spectra, 29:44-47 conjugated complexes, 40:98-99 W(CO)(EtC-Cet),, pseudotetrahedral, crystal structures, 40.98-100 293-4 history of study, &46 333 Ultraviolet spectroscopy

nonconjugated complexes, &99-101 U six-and seven-coordinate complexes acyl complexes, synthesis, a73 Ullmann reaction, 12:301-303 anionic oxygenfsulfur donor ligands Ultrasound, see also Sonochemistry and synthesis, 40:73-74 application to Simmons-Smith cyclopropa- catalytic activity, a74 nation of olefins with zinc-diidometh- ane, 25108-109 crystal structures, 4048, 51-53, 57- 58,68,73-74 chemical effects, aqueous sonochemistry, 2592-93 halides as oxidizing agents, &67-69 in colloidal Na production, 25107 intramolecular oxidation of zero-valent effects on complexes, &69-70 heterogeneous catalysis, 25110-111 iodine compounds as oxidizing agents, liquid-solid heterogeneous organometal- 40:67 lic reactions, 29104 metal carbonyl fluorides, synthesis, zinc reagents, 25107-108 4070-71 in heterogeneous systems, 25104 metal halocarbonyls, reactions with neu- induction of ligand dissociation, tral donor ligands, 4071-72 2596-101 photochemical oxidation reactions, 4066 initiation of homogeneous catalysis, seven-coordinate complex, reaction with 25101-103 donor ligands in liquid-liquid heterogeneous systems, alkyne reactivity, 40:87 25103-104 antimony donor ligands, 4062 in lithiation reactions, 25104-106 arsenic donor ligands, 4062 mechanisms, 2574-84 bidentate nitrogen-sulfur donor li- cavitation at surfaces, 2582-84 gands, 40:64-65 cavitation in homogeneous media, bismuth donor ligands, 40:61-62 2576-82 nitrogen donor ligands, 4058-59 nonaqueous sonochemistry, 2594-95 oxygen donor ligands, 40:62,65 nucleation of cavitation, 2575-76 phosphorus donor ligands, 4059-62 Ultraviolet spectra sulfur donor ligands, 40:63-65 cobalticinium salts, 10:91 structural geometry, 4&47-48 cyclic arsines, 4225-227 synthesis, halogen oxygenation of car- cyclobutadiene complexes, 4118 bony1 complexes with donor ligands ferrocenes, 1090 arsenic donor ligands, 4055 hexaphenyldigermane, 444 bidentate nitrogen donor ligands, organoarsenic compounds, 4:223-227 4050-51 organopolysilanes, 680-85 4:44 bidentate phosphine ligands, 4054-55 perphenylated cyclogermanes, polyplumbanes, 471 butylisonitrile, 4050 polysilanes, 426-28 halide ligands, 40:48-50 pseudohalides, 5180-181 monodentate nitrogen donor ligands, silenes, 2516-17 40:50,56 triorganostibine sulfides, 14:193-194 monodentate phosphine ligands, ylides, 20129-130 4053-54 Ultraviolet spectroscopy oxygen donor ligands, 4055-56 arsasilenes, 39221 seven-coordinate complex synthesis, digermenes, 44:134 40:56-58 germanethiones, germaneselones, and ger- sulfur donor ligands, 4056-58 manetellones, 44:162 tridentate nitrogen donor ligands, germanium doubly bonded compounds, 4051,53 39285-286 Ultraviolet spectroscopy 334

phosphasilenes, 39206 Ureylene complexes, 10121 silenes, 3997-99 UV spectroscopy, see Ultraviolet spec- tin doubly bonded compounds, troscopy 39:308-309 UV-visible spectroscopy Ultraviolet-visible spectroscopy, germenes, of bis(trimethylsily)diazene, 23143 &121 of end-on C,O-bonded carbonyls, 23:239 1,5,10-Undecatrienes, from butadicne and and redistribution reactions, 23100-101 methacrylic ester, 878-79 Unhindered ketone, addition of Grignard, k237 V Unsaturated ethers, hydroformylation, Vacuum gas solid reaction, 39162 1242-44 Valence tautomerism, 3159-161 a,P-Unsaturated ketones, reactions with or- cyclooctatetraene iron carbonyl com- ganocopper compounds, U290-293 plexes, 4378-379 a. P-Unsaturated species a-tropylium metal carbonyl complexes aldehydes cobalt, 4:360 hydroformylation, 1233-47 iron, 4359 selective hydrogenation, 12332 molybdenum, 4:357-358 carbonyls, asymmetric hydrogenation, Vanadaindane, stability, 42165 12354-355 Vanadium carboxylic acids, asymmetric hydrogena- carbenes, 32272 tion, 12342,356-357 carbonyl derivatives, 3195-196 ketones mixed alkali metal compounds, 22252 asymmetric reduction of C=C bond, pentacarbonylmetallate anion, see Penta- 12357-358 carbonylmetallate(3-) of vanadium hydroformylation, 1233-47 ylides, 14236-237 reduction of C=C bond via hydrosila- Vanadium, anionic hydride complexes tion, 12337 reactions, 2228-29 Uranium borohydride, 1k4 with acid halides, 2241-42 Uranium complexes with alkyl halides, 2235-41 adduct of cobalt cluster, 23267 with small electrophiles, 2234 allyl, as Ziegler-Natta catalyst, 18125, spectroscopic properties, 27:4, 6, 23-25 7 30 structural characteristics, 2%11 borane, 2k63 Vanadium carbonyls bridged lithium derivatives cationic derivatives, 8131-133 chloride, 24441 as an oxidizing agent, 8129 with 0, N-donor ligands, 24438 cyclopentadienyl vanadium carbonyl de- electron-transfer reactions rivatives, 2:181-182 bis(cyclooctatetraene), 2366 , 2178-181 cyclopentadicnyls, 23:63 Vanadium complexes, 8216-218 isocyanide, 1k81 acyclic pentadienylmetal, 26:136-137 via metal atom synthesis, 1588 bonding parameters, 26140 photochemistry of cyclopentadienylalkyIs, alkynyl, 3889, 112-113 24~253-254 arene, 1358-60, 64 Uranium, organo derivatives benzyne allyl compound, 9386 reactivity, 42164- 165 borohydride, 9:384 synthesis, 42:163 cyclooctatetraene complex, 9385-386 carbon dioxide insertion, 22151 cyclopentadienyls, 9:382-385 carbonyl diazene, 3498 Urea formation. 28186 carbonyl substitution mechanisms, 2k115 Vinyl carbenes

effect of a-bonding, 21:122 polymerization of higher a-olefins, and ion pairing, 2k122 18129 cyclopentadienyls and polymer stereoregulation, alkyl transfer reactions, 23122 18:108-109 ll-C,O-bonded binuclear carbonyl, Vanadocene, synthesis, 2381-382 23:275 Vaska’s complex, 5232, 35229 reactions with bis(trimethylsily1)dia- Vaska’s complex [(Ph,P),Ir(CO)CI] zene, 23182-183, 186, 188 nitrogen complex, 284 of 1,4-diaza-l,3-butadienes,21:170 oxidative addition reactions, 259-61, 70, electron-transfer reactions 72, 76, 79 bis(arene) derivatives, U92 acetylenes, 265-67 cyclooctatetraenecyclopentadienyl, hydrogen, 259,68 U97 kinetics, 258, 164 cyclopentadienyl cluster, U111 olefins, 265 fulvalene derivatives, U94-95 oxygen, 259, 63-64 phosphorus-bridged carbonyl, U99 stereochemistry, 260-61, 81 trinuclear arene halides, a111 Vaska’s compound, 36:72-73 electron-transfer reactions, 7-arenes, Vaska’s compound [(Ph,P),Ir(CO)CI], reac- 2363, 67 tion with diazomethane, 9422 aryls, 2334 V(CO)i, 3354, 56, 61, 63-64 Vibrational frequencies, silenes, 2520 cyclopentadienyls, 2345-46 Vibrational spectra hexacarbonyl, 234-5,292-293 bond strength, k308 mediation by CO ligands, 23:293 phosphine methylenes, 9297 sandwich compounds, 2363, 66-67 symmetry force constants, k309 vanadocene, 2366-67 thermodynamic function, k311 hexacarbonyl, reaction with liquid ammo- Vibrational spectroscopy nia, 1821 alkynyl-metal complexes, 38120-139 isocyanides, 22220-221, 229, 231, 243 disilenes, stable, 39243 main group, tellurium, 3k154-155 manganese-and rheniumpentacarbonyl al- via metal atom synthesis, 1589 kyls, 32179-180 nitrosyls polystannanes, 38199-202 carbonyl anion, 24.47 Vicinal dibromide, 28:101-102 cobalt clusters, 2448, 51 reduction with organotin hydride, pentacarbonyl trianion, 189 k73-74 phenylethynyl, 38122, 136 Vicinal dimesylates, 28:102 photochemistry of bis(cyclopentadieny1)di- g,,a-Vinylarene diiron complexes, 32300 methyl, 24272-273 Vinylboranes, 39356, 359, 364-366 terminal Z-C,O,bonded carbonyls, v’-Vinylcarbene complexes, in vinylketene 23244-245 synthesis, a333 tetracarbonyl vinylcyclopentadienyl, 2-Vinylcarbene complexes 2k42-43 in vinylketene synthesis, basic reaction, tetrahydroborate, 2k63 44:319-324 tricarbonyl cyclopentadienyl anion, 189 in vinylketene synthesis from trimetallic, 32287 acylferrates, 44:324-325 trimethylsilylnitrenes, 23188-189 v’-alkynylcarbenes, 44:325-326, triple-decker cyclopentadienyl, 30217 328-330 122-valence electron, 30204 v4-vinylketone complexes, 44:333-350 in Ziegler-Natta catalysis, 18125 p,$-Vinylcarbene complexes, 20219 activity loss on reduction, 18130 Vinyl carbenes, 3251,71 Vinylchlorosilanes 336

Vinylchlorosilanes, addition of t-butyllith- from carbynes, 2267-68 ium, 3974, 77, 93 from metal acetylides, 2264-66 Vinyl compounds from metal acyls, 2268-69 main group derivatives, 1034 from u-vinyls, 2266-67 organometallic, 10262 reactions, 2269-74, 81-82 reactions with BZC14and BZF4, addition of &carbon atom, 2273 10257-259 deprotonation, 2273 tin compounds, 10261 ligand exchange, 2274 Vinylcopper compounds, 12.229 nucleophilic addition to a-carbon, Vinylcyclohexene, synthesis, 834-35, 54-59 2269-73 Vinyldisilanes, 3974, 79 protonation, 2274, 81-82 Vinylferrocene, 32134 relationship to other q'-carbon bonded li- Vinylgallium compounds, &I87 gands, 22112-113 Vinylhalosilanes, t-butyllithium added to, structures, 2299-103 39114 binuclear, 22101-102 Vinylidene mononuclear, 22100-101 coordinated ligands, nucleophilic addition p-Vinylidene complexes, 20161 to, 25138-140 bonding, 20199-200 formation from transition metal carbynes, NMR spectra, 20213 2295-97 X-ray structural data, 20208 Vinylidene complexes, 2260-82, 87-124 Vinyl isocyanide complexes, with manga- alkyne polymerization, 295 nese, 1k57 bonding, 2297 MO calculations, 2298-99 v4-(Vinylketene)chromium(O) complexes, al- as intermediates, 22:93-96 kyne annulation, 44:278-287 in c+-acetylidenesynthesis, 2293-94 v4-(Vinylketene)cobalt(I) complexes, synthe- to alkoxy(alkyl)carbenes, 2294-95 sis from in cycloaddition of carbondiimides, carbenes, 44:298-300 2295-96 cobaltacyclobutenes, 44:301-302 in protonation of u-acetylides, 2294 cyclobutenones, 44:302-307 IR spectra, 2299, 104-109 cyclopropenes, 44:300-301 "C NMR spectra, 2297, 104-107 free vinylketene, 44:307 photochemistry, 24:327-340 Vinylketene complexes, 3267, 71 physical properties, 2299, 104-109 decarbonylation, 2&48 binuclear species, 22108-109 formation, 2&30-31 mononuclear species, 22104-107 nucleophilic reactions, 2851 polynuclear complexes, 22115-122 type VII, 2819-20 preparation of binuclear species, v4-(Vinylketene)iron(O) complexes 2275-81 synthesis by insertion into cyclopropenes, from alkynes, 2277 44:308-319 via bridge modification, 2279-81 synthesis from from 1,l'-dichlorocyclopropanes, acylferrates, 44:324-325 2278-79 v'-alkynylcarbenes, 44325-326, from 1,l'-dichloroolefins, 2278 328-330 from diphenylketene, 2276-77 free ketene, 44:330-331 from mononuclear species, 2275-76 2-methoxyallyl halides, M330 preparation of mononuclear species, propargyl-iron complex, 44332 2262-69 3-vinylcarbene complexes, 44319-324 from alkynes, 2262-64 v4-vinylketone complexes, 44333-350 from carbenes, 2267 vinylstannanes, 44:333 337 Water-gas shift reaction v4-(Vinylketene)manganese(I) complexes, mechanism, 1k276-278 synthesis, U297 Voigt-Reid equation, 34:166 v4-(Vinylketene)molybdenum complexes, Volatility synthesis from Group 2 compounds as precursors for (1,2,3-9)-frans-butadienylcomplexes, chemical vapor deposition, 40:218- 44:290-294, 296 219,223-224, 327-328 cyclopropenes, 44.289-290 substituents effects in metallocenes, (1,4-$)-vinylketone complexes, U296 40:129-130 Vinylketenes VSEPR model, 35250 circular dichroism spectra, 44:348-349 free, in vinylketene synthesis, a307 v4-(Viny1ketene)tungsten complexes W synthesis by carbonyl insertion, Wacker process 44:2 8 8 - 2 8 9 and CNDO calculations, 16:253-254 synthesis from mechanism, 13378-385 (1,2,3- 9)-trans-butadienyl complexes, stereochemical considerations, U290-294, 296 13443-444 cyclopropenes, 44:289-290 Wade's rules, X24-25 (1,4-$)-vinylketone complexes, M296 Wagner-Meerwein rearrangement, 16131, v4-(Vinylketene)vanadium(I) complexes, 168 synthesis, a297 Walden cycle, and chiral manganese ni- v4-Vinylketone complexes, in vinylketene trosyl cyclopentadienyls, 18174 synthesis, M333-350 WALTZ pulse sequence, 28:424 (1,4-3)-Vinylketone complexes, in vinylke- Water tene synthesis, 44:296 alkyl halide-metal reaction, 3870-71 Vinyl-lead compounds, 7~259-260 reaction with germenes, U125 Vinyl ligands, 32224-229 as solvent, 38155-156 $-Vinyl ligands, formation, 2971-83 supercritical, 38184 Vinyl-metal compounds, 332-35 Water-gas shift catalysis, 34245-250 Vinyl osmium(I1) complexes, 29200-201 dihydrogen production, 34245-246 Vinylpolysilanes, copolymerization, 6:79 rhodium complexes Vinyl radical, reaction with Sn hydrides, catalytic cycle, 34:248 U94 efficiency, 34247 Vinylsilacyclobutanes, silenes from, 3977, metallic centers, synergism between, 93,105 34247 Vinylstannanes, in vinylketene synthesis, water-gas shift reaction, 34246-247 44.333 ruthenium complexes, W.249-250 Vinylthallium compounds, 8191-192 Water-gas shift reaction, 3595-104, 38177 Vinylzirconocene complexes, 32225 catalysis Visible spectra, see Electronic spectra in acidic solutions, 28191, 196-197 Vitamin B12, 1325, 33, 38161-162 in alkaline solutions, 28187-194 reactions, 2203 in aqueous organic amine solutions, with isocyanides, 11:63 28:190,194-195 structure, 1k332 of binary metal carbonyls, 28182-183 Vitamin BI2coenzyme by copper complexes, 22143-144 cobaloximes as models, 16:276-278 in neutral solutions, 28191, 196-197 ESR studies of active site, 14369, 389- by rhodium complexes, 22:142-143 390,392 catalysts for, 28198 homolysis of Co-alkyl bond, 14389-390 cycle, 221 u-n rearrangements, 16275-278 decarboxylation and, 2tk179-180 Water-gas shift reaction 338

and importance of nucleophilic activation tion reactions with electron-rich al- of homogeneous catalysis, 28140 kynes, 43182-183 rhodium complexes, 34246-247 [W(CO)s(S=C(C,H,NMe,-p)Hll Water-soluble ligands nucleophile reactions, 43175 in homogeneous catalysis, see Homoge- synthesis, a164 neous catalysis, water-soluble ligands [W(CO),(S=C(C,H,R-p)PhJ1,71'-E/q'-Z in isomerization, 43134 miscellaneous studies [W2( CO) ,,,Se4][ AsF& synthesis and struc- carbonylations, M272-273 ture, 4k244-245 oxidations, 34:274 [W(CO)s(Se=C(Ph)2)],synthesis, 43187 photocatalytic reactions, 34277-278 [W( CO),{ Se=C( Ph)C6H4R-p]], cycloaddi- substitutions, 34274-275 tion reactions with conjugated dienes, support immobilization, 34275-277 43180 telomerizations, 34273 [{W(CO)3]6Te2)4]2-,synthesis and structure, unsaturated compound addition, 4k259-260 34270-272 [W(CO),(Te=C(Ph)H)], cycloaddition reac- preparation tions with conjugated dienes, 43179 aminated phosphines, 34224-226 [W(CO)sW(S=C(Ph)H)Mn(CO)2,(v5- carboxylated phosphines, 34:227-228 CsH,)], synthesis, 43168 chiral ligands, 34:228-233 White phosphorus, reactions with nitrogen containing, 34233-234 arsasilene, 39223 phosphines disilenes, 39266-267 ether functional group, 34226-227 phosphasilene, 39210-211 hydroxyl functional group, Whitesides synthesis, 34221-222 34226-227 Wiberg silenes, reactions with sulfonated phosphines, 34220-224 dienes, 39:112, 117 NMR spectroscopy, 34223-224 quadricyclane, 39120 reactivity. M224 Wide-line NMR techniques, 912-15 Whitesides synthesis, 34221-222 Wilkinson's complex [Ph3P)3RhCI], 285 transition metal complexes addition of hydrogen, 1:69 aminophosphines, 34.241-242 catalytic decarbonylation, 288 non-phosphorus complexes, 34242-245 hydrogenation, 285 absorptions, 34243 Wittig chemistry, of tungsten alkoxides, coordination numbers, EDTA com- 22319-320 plexes, 34244 Wittig reaction, 20115-116. 119, 26:147, NMR data, 34243 153, 34140 precursors, M244 in p-methylene synthesis, 20183 preparation, 34242-243 Wittig rearrangement, 162-3, 18-24, 162, stability constants, 34245 168 phosphines of organogermyl alkoxides, 1619-20 carboxylic functions, 34239-241 of organosilylalkoxides, 16:18-24 ether functions, 34239-241 mechanism, 1624 hydroxy functions, 34239-241 relationship of a-silyl carbinol re- sulfonated phosphines arrangement, 16:20-22 IR spectra, 34235-236 stereochemistry, 1622-24 NMR data, 34237 Wolff rearrangements, silenes, 39147-148 synthesis, 34234 Woodward-Hoffmann rules [W(CO)(H-C=C-BU')~(E=C(P~)H)],syn- and C-C coupling reactions, 12199 thesis, 43184-185 in organometallic chemistry, 151 [W(CO),(~'-S=C(C~H.1R-p)H)],cycloaddi- and $-polyene complexes, 1528-29 339 Ylides

and polyhapto organotransition metal methyltrioxorhenium(VII), 41:132-133 complexes, 16223 organoplatinum(1V) compounds, and rearrangement of organo-Group 111 22122-123 compounds, 1671-72 X-ray diffraction and 1,2-sigmatropic shifts, 162 arsalienes, 39225-226 silenes, 39104 main group-transition metal clusters, Wurtz coupling, 4278-280 42128, 130 Wurtz-Fittig reaction, 4149 phosphasilenes, 39:206-208 structural properties of Group 4B metal- locene dicarbonyls, 25351 x tropyne-transition-metal complexes, X-ray crystallographic studies 42185 acetylene complexes, 1455-57, 247, 1520 X-ray diffraction analysis variation of C-C-H bond angle, 1520 germanetellones, 4k159-161 alkylidynetricobalt nonacarbonyls, 1499, monocyclic A5Si-silicates with, SiO,FC, 110 skeleton, 4k266 alkyltin halides, 1467-69, 71-72, 78, 83- spirocyclic A%-silicates 86, 89 with Si04Cskeleton, with allene complexes, 14265-267, 271 benzene-1,2-diolato(2-) bidentate li- bridged electron-deficient aluminum com- gand, 44:230-233 pounds, 15241, 248-249 ethane-1,2-diolato(2-) bidentate li- criteria for accuracy, 1437-38 gand, 4k239-240 diazene complexes, 1457 ethene-1,2-diolato(2-) bidentate li- high nuclearity metal carbonyl clusters, gand, 4k236-237 14286-306.327 whydroxycarboxylic acids, imine complexes, 1458 4k245-246 ketone complexes, 14:57-58 naphthalene-2,3-diolato(2-) biden- metailocarboranes, 14148, 155-156, 168, tate ligand, 44230-233 174, 178 salicylato(2-) bidentate ligand, olefin complexes, 1437-55,1519-24 4k252-254 bending back of substituents, 1519-21 with Si02N2C skeleton, 4k257 C=C bond lengths, 1519 with SiO&C skeleton, 44.260-261 conformational preferences, 1519, 21 with SiOs skeleton, 44:262-263 phosphorus ylides, 14211 platinum ethenol complex, 16250-252 Y P-interaction, 16250-252 six-coordinate methylantimony com- Yb[C(SiMe&, synthesis, 43285 pound, 14189-190 Ylid complex, structure, 5113 tantalum-ylide complex, 14239 Ylide carbanions, as reaction intermediates, X-ray crystallography a298 alkynyl-metal complexes, 3890-120 Ylide complexes amino(1-alkynyl)carbenes, 41:170 from phenylcarbene complexes, 12463 chalcogen-bridged metal-carbonyl com- of rhodium as hydrogenation catalysts, plexes, 41:244248, 250-253, 255- 12372 256,258-264,266-272,274-279,281, Ylides 283-284,287,289,292-293,295-310 ammonium, 14208 cobalt-alkyne complexes, 41:76-77, 82- antimony, 14231-232 83, 89-90, 94-96 arsenic, 14224-229 cycloreversion of rhenium diolates, donor properties, 14206 41:150 metalated copper complex, a230 Ylides 340

nitrogen, 14207-209 NMR spectra, M134 phosphorus, 14209-214 similarity to lanthanide complexes, 24134 tantalum, 14238-239 Yttrium compounds, mixed alkali metal, transition-metal, relationship with car- 27:215, 256 bene complexes, 14240 vanadium, 14236-237 Ylids, 1331 Z Ytterbium complexes alkyls, U136-137 Zaitsev reactions, U104 aryls, 24136,154 Zeise’s dimer, 352, 6 bis(cyclopentadieny1) derivatives Zeise’s salt, 1:240, 13:19, 1407 acetylide-bridged dimer, 24143 diffraction studies, 1517 solvated monomer, M140 MO calculations, 156, 14-17 divalent compounds olefin substitution reactions, 10361 alkynides, M154 reactions with organosilyls, 15120-121 cyclopentadienyls, 24158-159 Zeolite complexes, 22236-238 halide-bridged lithium derivative, Ziegler catalysts 24436-437 in ethylene-propylene copolymerization, methyl-bridged cyclopentadienyl dimer, 12270 24139 in hydrogenation of aromatic hydrocar- hydrogenolysis, 24141 -142 bons, 12376 photochemistry, 24255 in hydrosilation, 12430-431 pentamethylcyclopentadienyls, U161, and olefin polymerization, k182-185 165-167 Ziegler-Natta catalysis, 1899-149 divalent compounds, 24165 and gas-phase polymerization, 18106-107 one-electron oxidation, 24:166 homogeneous systems, 18123-143 phosphine derivatives, a166 cyclopentadienyl zirconium complexes, reaction with metal carbonyls, 18132-135, 140 24:166-167 dicyclopentadienyl titanium systems, tris(cyclopentadicnyl), reaction with al- 18124-129,135-139 kynes, 24143 effect of water, 18:137-143 zero valent cyclooctatetraene compounds, side reactions, 18131-137 24155 vanadium complexes, 18125, 129-130 Ytterbium compounds magnesium-titanium catalysts, 18120-123 cyclopentadienyl amide, 9:369 mechanism Grignard analogs, 9366 chain propagation, 18103-104 mixed alkali metal, 22209 chain termination, 18103-105 Ytterbium, cyclopentadienyl complexes insertion of monomer into metal-car- adducts with metal carbonyls, 23240-241 bon bonds, 18101 in CO mediated electron-transfer, 23296 monomer adsorption, 18101 oxidation, 2363 and stercoselcctivity, 18108-114 as reducing agents, 23296 and molecular weight of polymer prod- Yttrium complexes ucts, 18105 alkyls, U136-137 decrease by hydrogenation, 18103-105 bis(cyclopentadieny1) derivatives distribution and surface heterogeneity, and alkene hydrogenation, 24152 18116-117 alkylideneamido complex, U150-151 origin of catalyst activity, 18114-118 alkyls, 24143 formation of propagation centers, hydride dimer, U145, 150-151 18117 hydride trimer, 24:148-149 number of active sites, 18:114-115 341 Zindsilver-graphite

and solid-state structure of titanium tri- configuration of initial catalyst, 16:257 chloride, 18114-116 mechanism, 16:256-259 polymer stereoregulation, 1899-101, role of u-rr rearrangements, 16256-259 108-114 Zinc and cis addition to double bond, alkyls, bond dissociation energies, 2105 18109,111-112 dialkyls, 135-6 and chirality of active center, diethyl, 321 18111-112 dimethyl, methane formation with tung- and chirality of growing chain, 18:109 sten hexachloride, 17:453 for dienes, 18113-114 methyllithium derivative, 24394 and metal substitution, 18109 mixed alkali metal compounds, 22219- via titanium catalysts adsorbed onto 220,222,247 magnesium compounds, 18121 reaction of metal atoms with alkyl ha- by vanadium catalysts, 18108-109 lides, 1579 process operation, 18105-108 reaction with alkyl halides, 3873 second-generation catalysts, 18102-105 reagents, ultrasound effects, 25107 supported catalysts, 18119-122 Zinc carbenoids, see also Organozinc com- tailoring of heterogeneous catalysts, pounds 18118-123 reactions with allenes, 12.101 aging, 18:118 18115 aromatic carbon-carbon bonds, by milling, 1297-99 optimum catalyst components, 18:119 carbonyl groups, 1299-100 use of single crystals, 18119 iminoester, 12101 Ziegler-Natta catalysts, 1511 discovery, 6:11 unsaturated bond, U100-101 U85-97 polymerization reactions, 6:12 in synthesis of cyclopropanes, Ziegler-Natta olefin polymerization in transfer reactions with olefins active cationic species, 32327-328 alkylidene transfer, U93-94 A1 cocatalyst, role of, 32327 arylmethylene transfer, 12.94-95 Cp*MMe/alumina catalysts, NMR studies, halornethylene transfer, l2:95-96 32372-373 methylene transfer, U85-93 CpaMMe/MgClz catalysts Zinc complexes ethylene, exposure to, 32:372-373 acyclic pentadienyl, 26:130-131 NMR studies, 32372-373 reaction with electrophiles, 26:132 CpzMX2/alumoxane catalysts anionic hydride, spectroscopic properties, cation systems, comparison to, 32371 226 mechanism, 32373-374 boranes, 2k63,66,70 notable features, 32370 carbyne, reactions with acetylenes, 2291 X-ray photoelectron spectroscopy, 1,4-diaza-1,3-butadienes 32:371-372 with chelate ligand, 2k167-169,193 [Cp2Ti][A1C14],isolation of, 32328 dimerization, 2k214-216 early-metal metallocene alkyl complexes, ESR spectra, 2k215-216 studies of, 32329 ligand activation, 21:221-223 historical interest, 32327-329 radicals, 2k213-216 mechanism, 32327 phenylethynyl, 38122, 135-136 reactions involved in, 32328 trimetallic, 32287 soluble catalyst systems, 32328 Zinc-graphite, 281 13-1 15 Ziegler-Natta polymerization, 26:185, 189, Zincocene, substituent effects on structure, 36:46, 48 40.144 Ziegler-Natta process, 16:256-259 Zinc/silver-graphite, 28:116-118 ZINDO 342

ZINDO, nonlinear optics calculations, tetracarbonylmetallate(4-) anion, 42311, 314-315, 348, 3.53-354 3k39-45 Zintl anion, 39:26 tetrahydroborates, 21:63, 104 Zintl ion tricarbonylmetallate(6-) anion, 3k45-46 applications, 42:43-44 trimeric yttrium cyclopentadienyl hy- main group-transition metal cluster syn- dride, a149 thesis, 4287-88 tropyne, synthesis and reactivity, 42183 Zirconium 128-valence electron, 30201-204 bis( q-cyclopentadieny1)dicarbonyl- Zirconium complexes, photochemistry zirconium formation, 25333-336 bis(cyclopentadienyl)alkylalkenyls, bis( q-pentamethylcyclopentadienyl) 24269-271 dicarbonylzirconium, 25338-341 isomerization, 24269-271 functionally substituted h-cyclopentadie- bis(cyclopentadieny1)alkyl halides, nyl dicarbonyl complexes of Ti and 24268-269 Zr, preparation, 25345-346 bis(cyclopentadienyl)dialkyls, 242260-263 ( v-CZMes)CpM(CO)2preparation, 25342 with alkynes, 24:261 mixed alkali metal compounds, 27251 with CO, 2263 Zirconium complexes, 8214-215 dimethyl, 24260 acyclic pentadienyl, 26138, 143 with ethylene, 24262 alkyl, 38108-109 bis(cyclopentadienyI)diaryls, 24264-268 alkynyl, 38108- 109 with alkynes, 24.268 arene, 1358 aryl coupling reactions, 24:264-267 benzydiyne, synthesis and reactivity, with dienes, 24267-268 42:175-176 hydride formation, 24:265 benzyne pentamethylcyclopentadienyls, a266 cyclometallation, 42158-160 dialkyl, 24:258-259 3,4-disubstituted indole synthesis, tetraalkyls, 24:255 42160, 162 and styrene photopolymerization, synthesis, 42156-157, 163 24255-256 bimetallic, 37:225-226, 228, 254, 262-265, Zirconium complexes, as Ziegler-Natta cata- 271-272, 277-280,282, 302-303 lysts, 18132-135 catalyzed reduction of CO, 1273 dicyclopentadienyls, 18132-135 cycloheptadienyne, synthesis, 42194 mechanism of action, 18132-135 cyclohex-3-eneyne, synthesis, 42191 structure of alkylaluminum adducts, cyclohexyne, synthesis and reactivity, ltk134-135 42:189 tricyclopentadienyl aluminum adducts, p-ethylene, 20237-238 18:135-140 fluoroalkyl, 3k188 Zirconium, cyclopentadienyl complexes formyls, 2031-33 adducts of metal carbonyls main group, tellurium, 3k154-155 cobalt, 23267,270-271 naphthalyne, synthesis and reactivity, molybdenum, 23271-272 42178-180 alkyl transfer reactions, 23122 phosphaalkyne, W212-213 electron-transfer reactions platinum heteronuclear cluster, alkyls, 2943-44 31:380-383 halides, 2341 propargyl, structure, 37:83, 86 mediation by CO ligands, 233295 reduction of coordinated CO by hydro- Zirconium dichloride, dicyclopentadienyl, gen, 17:70-72 fragmentation pattern, 6287 mechanism, 1771-72 Zirconium, dicyclopentadienyl complexes, of substituted cyclopentadienyls, 2k37-38 19:l-50 343 Z-scan

alkyldinitrogen derivative, 1922 and molar ratios, 2429 binuclear p-naphthyl-p-hydride, 1915-1 6 temperature effects, 24:29 binuclear tris(dinitrogen) compounds, reactivity, 2426-33 1914,29-39,43 with aldehydes, M30-33 hydrazine formation with HCI, 1930 with ethylene, 24:28-30 reaction with ethylene, 1943 isomer effects, M26, 28 structure, 1929-30 with ketones, 2430-33 bis(borohydride), 19:36 structural comparisons dicarbonyls, 1936 of cis and trans isomers, 224 reaction with carbon dioxide, 1938 with free dienes, 2424 and reduction of CO to methanol, with hafnium complexes, M21-24 1938-39 of tetramethyl -3,4-bis(methylene)tricyclo- dichloride, reduction, 1915 hexane dimethyl, photolysis, 198, 15 isomerization, M9-11 metallacycles, 1943-44 variable temperature NMR spectra, metallacyclopentane, 1943 24~9-10 reaction with CO, 1943 thermodynamics of isomerization, 24:s-9 permethylzirconocene, 1914 effect of diene substituents, M8-9 zirconocene, 192,14-15 s-trans-isomers Zirconium hydride, 37:225 via alkenyl coupling, 244, 7 Zirconocene, 37:262-263 of butadiene, M25 Zirconocene dichloride, 39330-331 from butadienemagnesium, 245-6 Zirconocene (.ri’-diene) complexes and $-complexes, M4 carbon-carbon coupling reactions, 2428- of diphenylbutadiene, 247, 25 30, 32 electronic spectra, M13 equilibrium with cis-isomer, 244, 8 carbonylation, 2426-28 via metallacycle, 24:6-7 cyclopentanone formation, 2427-28 NMR spectra, 2413-15 effect of diene, 2427 as olefin r-complex, 2426-28 rate effects, 2427 photoelectron spectra, 24:13 s-cis-isomers via radical-induced ligand exchange, asymmetric diene bonding, 2417 247 automerization, 24:ll-I3 structures, M24-26 2,3-dimethylbutadiene structure, MI9 synthesis, M4-7 dynamic behavior, M9-13 tetrakis(methy1ene)bicyclo [2.2.2] oc- electrophilic attack, 2430 tane, 247 isomerization, M8-9 Zirconocene monocarbonyl derivatives, mo- metal alkyls, M26, 30 nocarbonyl complexes, formation, MO calculations, 2419-20 25365-371 NMR spectra, M13-15 Zirconocycles, 39331 photoelectron spectra, 2413 Zirconoindan complexes u,n-bonding, M17-18, 24 degenerate ring inversion, M12 as 2,r-complexes, M18-19, 21 structure, M16, 18-19 structures, 2413, 15-21 Zirconoindane, stability, 42165 energy profile for butadiene derivative, Zirconole, synthesis, 39330 M4 Zirconoxycarbene complexes, 32272 reactions with ethylene, M28-30 Z-scan, third-order nonlinear optics analy- isomer effects, 2428 sis, 43361-363 Cumulative List of Contributors for Volumes 1-44

Volume numbers are in boldface

Abel, E. W.,51, 8117 Bruce, M. I.,6273, 10273, 1k447, 12:379, Aguil6, A,, 5321 2259 Akkerman, 0. S., 32:147 Brunner, H., 18151 Al-Ahmad, S., 39325 Buhro, W. E., 22311 Albano, V. G., 42285 Byers, P. K., 341 Alper, H., 19183 Cais, M., 8211 Andersen, J.-A. M., 32169 Calderon, N., 12449 Anderson, G. K.,2039, 351 Callahan, K. P., 14145 Angelici, R. J., 2251 Canty, A. J., 341 Aradi, A. A,, 30189 Cartledge, F. K., 41 Armitage, D. A,, 51 Carty, A. J., 3239 Armor, J. N., 191 Chalk, A. J., 6119 Ash, C. E., 27:l Chanon, M., 26165 Ashe 111, A. 5.,30:77, 39325 Chatgilialoglu, Chryssostomos, a67 Atwell, W. H., 41 Chatt, J., l2:l Aumann, R., 4M65 Chini, P., 14285 Baines, K. M.,251, 39:275 Chisholm, M. H.,26:97,27:311 Baker, P. K., 4046 Chiusoli, G. P., 12195 Barone, R., a165 Chojinowski, J., 30243 Bassner, S. L., 281 Churchill, M. R., 593 Behrens, H., 181 Coates, G. W., 9195 Belzner, J., 431 Collrnan, J. P., 253 Bennett, M. A., 4353 Compton, N. A., 3k91 Berry, D. H., 43197 Connelly, N. G.,231, 2487 Bertrand, Guy, a175 Connolly, J. W., 19:123 Bickelhaupt, F., 32147 Corey, J. Y., 13139 Birmingham, J., 2365 Corrigan, J. F., 3239 Blinka, T. A,, 23193 Corriu, R. J. P., 20265 Bockman, T. M., 3351 Courtney, A, 16241 Bode, K., 4O:l Coutts, R. S. P., 9:135 Bogdanovic, B., 12105 Coville, N. J., 36:95 Bottomley, F., a339 Coyle, T. D., 10237 Bourissou, Didier, M175 Crabtree, R. H., 28299 Bowser, J. R., 3657 Craig, P. J., 1k331 Bradley, J. S., 22:l Csuk, R., 28:85 Brew, S. A,, 35135 Cullen, W. R., 4145 Brinckman, F. E., 20313 Cundy, C. S., 1k253 Brook, A. G.,295,251,3971 Curtis, M. D., 19:213 Brook, M. A,, 3971 Darensbourg, D. J.,2k113, 22129 Brothers, P. J., 39:l Darensbourg, M. Y., 221 Brown, H. C., 1k1 Davies, S. G., 30:l Brown, T. L., 3365 de Boer, E., 2115 345 346 Contributor Index

Deacon, G. B., 25237 Griffith, W. P., 2211 Deeming, A. J., 261 Grovenstein, Jr., E., 16:167 Dessy, R. E., 4267 Gubin, S. P., 10347 Dickson, R. S., 12:323 Guerin, C., 20265 Dixneuf, P. H., 29163 Gysling, H., 9361 Doherty, S., 3239 Haiduc, I., 15113 Driess, M., 39193 Halasa. A. F., 1855 Dyson, P. J., 4344 Hamilton, D. G., 28299 Eisch, J. J.,1667, 39355 Hampden-Smith, M. J., 40:215 Ellis, J. E., 3k1 Handwerker, H., 36229 Emerson, G. F.. k1 Hanusa, T. P., 40117 Epstein, P. S., 19213 Harrod, J. F.,6119, 42363 Erker, G., 24A Hart, W. P., 2k1 Ernst, C. R., 1079 Hartley, F. H., 15189 Errington, R. J., 3k91 Haubrich, Scott T., &1 Escudie, Jean, 44.1 13 Hawthorne, M. F., 14145 Evans, J., 16311) Hays, M. L., a117 Evans, W. J., 24131 Heck, R. F., 4243 Faller, J. W., 16211 Heiber. W., 81 Farrugia, L. J., 31:301 Heimbach, P., 829 Faulks, S. J., 25237 Helrner, B. J., 23193 Fehlner, T. P., 2k57 Hemme, I., 39:159 Fessenden, J. S., 18275 Henry, P. M., 13363 Fessenden, R. J., 18275 Heppert, J. A., 2697 Fischer, E. O., 141 Herberich, G. E., 25199 Fischer, H., 43:125 Herrrnann, W. A,, 20159 Fleig, P. F., a215 Hill, A. F., 36:131 Ford, P. C., 28139 Hill, E. A,, 16131 ForniCs, J., 12219 Hoff, C., 19123 Forster, D., 12255 Hoffrneister. H., 32227 Fraser. P. J., a323 Holzmeier, P., 3467 Friedrich, H, 36:229 Honeyman, R. T., 341 Friedrich, H. B., 33235 Hopkins, M. D., 3879 Fritz, H. P., k239 Honvitz, C. P., 23219 Frstner, A,, 2885 Hosmane, N. S., 3099 Furukawa, J., 1283 Housecroft, C. E.,2k57, 331 Fuson, R. C., k221 Huang. Y. Z., 20115 Gable, K. P., 4k127 Hughes, R. P., 3k183 Gallop, M. A., 25121 Humphrey, M. G.,42:291,43349 Garrou, P. E., 2395 Ibers, J. A., 1433 Gauvin, F., 42363 Ihmels, H., 431 Geiger, W. E.,231, 2487 Ishikawa, M., 1951 Geoffroy, G. L.,18207, 24249, 281 Ittel, S. D., 1433 Gibson, Susan E., &275 Jain, L., 22113 Gilrnan. H.,k89, 41, 7:l Jain, V. K., 22113 Gladfelter, W. L.,18:207, 2441 James, B. R., 12319 Gladysz, J. A., 201 Janiak, C., 33291 Glanzer, B. I., 2885 Jastrzebski, J. T. B. H., 35241 Green, M. L. H., 2325 Jenck, J., 32121 Grev, R. S., 33125 John, K. D., 3879 Contributor Index 347

Jolly, P. W.,829, 19257 Manuel, T. A,, 3181 Jomes, M. D., 27279 Markies, P. R., 32147 Jonas, K., 1997 Mason, R., 593 Jones, P. R., 15273 Masters, C., 1261 Jones, W. M., 42147 Mathur, P., 4k243 Jordan, R. F., 32:325 Matsumura, Y., 14187 Jukes, A. E., 12215 Mayr, A,, 32227 Jutzi, P., M217 McDonagh, A. M.,42291,43:349 Kaesz, H. D., 31 McGlinchey, M. J., 34285 Kalck, P.,32121, 34219 McKillop, A,, 1k147 Kaminsky, W., 1899 McNally, J. P., 301 Katz, T. J., 16283 Meister, G., 3541 Kawabata, N., l283 Meyer, R., 32219 Kawachi, A,, 381 Mingos, D. M. P., 151 Kernmitt, R. D. W., 22279 Mochel, V. D., 1855 Kettle, S. F. A., 10199 Moedritzer, K., 6171 Kilner, M., 10115 Molloy, K. C., 33171 Kim, H. P., 2251 Monteil, F., 34219 King, R. B., 2157 Morgan, G. L., 9195 Kingston, B. M., 1k2.53 Morrison, J. A,, 35211 Kirsch, H., 3467 Moss, J. R.,33235, 32169 Kitching, W., 4267 Mrowca, J. J., 2157 Klingebiel, U.,39159, &1 Mller, G., U1 Klosin, J., 42147 Mynott, R., 19257 Kochi, J. K., 3351 Nagy, P. L. I., 2325 Koster, R., 2:257 Nakamura, A,, 14:245 Kreiter, C. G., 26267 Nesmeyanov, A. N., 101 Krger, G., 241 Neumann, W. P., 2241 Kudaroski, R. A., 22129 Newcomb, Martin, 467 Khlein, K., 2241 Nienaber, H., 4k165 Kuivila, H. G., 1:47 Norman, N. C., 3191 Kumada, M.,619,1951 Ofstead, E. A., 12449 Lappert, M. F.3225, 9397, 1k253, Ogino, H., 42223 14345 Ohst, H., 25199 Lawrence, J. P., 12449 Okawara, R.,5137, 14187 Le Bozec, H., 29163 Okazaki, R., 39232 Lednor, P. W., 14345 Oliver, J. P.,8167, 15235, 1611 Linford, L., 321 Onak, T., 3263 Longoni, G., 14285 Oosthuizen, H. E., 22209 Lotz, S., 32219 Otsuka, S., 14245 Luijten, J. G. A., 3397 Pain, G. N., 25237 Lukehart, C. M., 2545 Parshall, G. W., 2157 Lupin, M. S., 8211 Paul, I., 10199 Macomber, D. W.,2kl, 25317 Peplow, Mark A., U275 Maddox, M. L., 31 Peres, Y., 32121 Maguire, J. A., 30:99 Petrosyan, W. S., 14163 Maitlis, P. M., 495 Pettit, R., k1 Mann, B. E.,12:135,28397 Pez, G. P., 191 Manna, J., 3879 Plm, Melanie, 4221 Manners, I., 32131 Poland, J. S., 9397 348 Contributor Index

Poliakoff, M., 25277 Sita, L. R., 38189 Popa, V., 15113 Skinner, H. A., 2209 Pourreau, D. B., 24249 Slocum, D. W., 1079 Powell, P., 26:125 Smallridge, A. J., 30:l Power, Philip P.,391, 44:l Smeets, W. J. J., 32147 Pratt, J. M., 11:331 Smith, J. D.,13453, 43267 Prokai, B., 5225 Speier, J. L., 12407 Pruett, R. L., 17:l Spek, A. L., 32147 Ranaivonjatovo, Henri, M113 Stafford, S. L., 31 Rao, G. S., 22113 Stanczyk, W., 30243 Raubenheimer, H. G., 321 Stibbs, W. G., 39275 Rausch, M. D.,2kl, 25317 Stone, F. G. A.,k143, 31:53, 35135 Reetz, M. T., 16:33 Stumpf, R., 43125 Reichl, J. A,, 43197 Su, A. C. L., 12269 Reutov, 0. A., 1463 Sun, S., a171 Rijkens, F., 3:397 Suslick, K. M., 2573 Ritter, J. J., 10237 Sss, Fink, G., 3541 Rochow, E. G., 91 Sutin, L., 2&339 Rokicki, A., 28139 Sweigart, D. A., 40171 Roper, W. R.,253,25:121 Swincer, A. G., 2259 Roth, G., 43125 Tacke, Reinhold, U221 Roundhill, D. M.,13273, 38155 Tamao, K.,6:19,381 Rubezhov, A. Z., 10347 Tate, D. P., 1855 Sakurai, H., 321 Taylor, E. C.. 1k147 Salerno, G., 12195 Templeton, J. L., 291 Salter, I. D., 29249 Thayer, J. S.,5169, 131, 20313, 3859 Samoc, M., 42291 Theodosiou, I., 2k16.5 Samock. M., 43349 Timms, P. L., 1553 Sappa, E., 3239 Tobita, H., 42223 Satge. J., 21:241 Todd, L. J., 887 Schade, C., 22169 Touchard, D., 29163 Schaverien, C. J., 36:283 Traven, V. F., 34149 Schemidbaur, H.,9259, 14205 Treichel, P. M.,1:143, 1k21 Schrauzer, G. N., 21 Tsuji, J., 17:141 Schubert, U., 301.51 Tsutsui, M.,9361, 16:241 Schultz, D. N., 18:55 Turney, T. W., 1553 Schumann, H., 33291 Twamley, Brendan, 44:l Schwebke, G. L., k89 Tyfield. S. P., 8:117 Sekiguchi, A., 321 Usdn, R., a219 Seppelt, K., 34207 Vahrenkamp, H., 22:169 Setzer, W. N., 24.353 van der Kert, G. J. M., 3397 Seyferth, D., 1497 van Koten, G.,21:151, 35241 Shapakin, S. Yu., 34149 van Rooyen, P. H., 32219 Shen, Y. C., 20115 Veith, M., 3k269 Shriver, D. F., 23219 Vezey, P. N., 15189 Siebert, W.,18301, 35187 von RaguC Schleyer, P.,24353,22169 Sikora, D. J., 25317 Vrieze, K., 21:151 Silverthorn, W. E., 1347 Wada, M., 5137 Singleton, E., 22209 Wagner, Brigitte, a221 Sinn, H., 1899 Wailes, P. C., 9135 Contributor Index 349

Walton, D. R. M., 13:453 Wiles, D. R., 1k207 Weber, L., 41:l Wilke, G., 8:29 Webster, D. E., 15147 Williams, R. E., 361 Weitz, E., 29277 Winter, M. J., 29101 Went, M. J., 4k69 Wojcicki, A.,ll:87, 231 Werner, H., 19155 Wojtczak, W. A., &215 West, R., 39232 Woo, H. G., 42363 West, T.,5:169, 161,23193 Yamamoto, A., 34111 White, D., 3695 Yashina, N. S., 1463 Whitmire, K. H., 422 Ziegler, K., 61 Whittall, 1. R.,42291, 43349 Zuckerman, J. J., 9:21 Wiberg, N.,23131, 24179 Zybill, C., 36229