APPENDIX

Introductory Lectures

1. "Introduction to the f-Elements", R. D. Fischer.

2. "Introduction to Organometallic Chemistry", T. J. Marks. Contributed Seminars

1. "Magnetic Properties of Trivalent Organometallic CompoWlds" , Reinhardt Klenze, Clemens M. Aderhold, and Basil Kanellakopulos, Kernforschungszentrum Karlsruhe, Institut fUr Heisse Chemie and Fachbereich Physikalische Olemie der Universitat Heidelberg, Federal Republic of Germany.

2. "Electrochemical studies on Uranocene", Jared A. Butcher, Jr. , James Q. Olambers, and Richard M. Pagni, Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37916, USA.

3. "Organoscandium Complexes Containing Large Organic Rings" , A. Westerhof, B. J. Roesink and H. J. de Liefde Meij er, Laboratoriu m voor Anorganische Scheikunde, RijksWliversiteit, Nijenborgh 16, 9747 AG Groningen, The Netherlands.

4. "Bis(pentamethylcyclopentadienyl) Alkyls: Facile Activation of Carbon Monoxide and Formation of Oxygen-Bonded Migratory Insertion Products", Juan M. Manriquez, Paul J. Fagan, and Tobin J. Marks, Department of Chemistry, Northwestern University, Evanston, IL 60201, USA; Cynthia Secaur Day and Victor W. Day, Department of Chemistry, University of Nebraska, Lincoln, NE 68588, USA. 5. "The Consistent Interpretation of the Spectroscopic and Magnetic Properties of Octahedral 5fl Halide Compounds of (IV), Uranium(V) and NeptWlium(VI)", K. Eichberger and F. Lux, Institut fur Radiochemie der Technischen UniversiUit Munchen, D-8046 Garching, Federal Republic of Germany.

6. "Synthesis and Spectroscopy of Indenyl Uranium(IV) Alkyls and Dialkyls" , Afif M. Seyam and Ghaida' Ala' Eddein, Department of Chemistry, University of Jordan, Amman, Jordan.

7. "New Synthetic Routes in ", J. C. Green, Inorganic Chemistry Laboratory, South Parks Road, Oxford, Great Britain.

B. "Recent Advances in Uranium(III) Chemistry", David C. Moody, Los Alamos Scientific Laboratory, University of California, Los Alamos, New Mexico 87545, USA. 497 498 APPENDIX 9. "Transferred Hyperfine Interaction Between the Rare-Earth Ions and Neighbouring Nuclei of Diamagnetic Ions in Simple Compounds Studied By NMR!I, Rolf Nevald, Laboratory of Electrophysics, 'll1e Technical University of Denmark, DK-2800 Denmark.

10. "An Isotope Effect in IH- NMR and Magnetic Susceptibility of Organo• metallic Uranium Compounds", R. v. Ammon, C. M. Aderhold and B. Kanellakopulos, Kernforschungszentrum Karlsruhe, Federal Republic of Germany. ll. "Uranium (V) and Uranium (VI) AIkoxides: Preparation, Properties, and Photochemistry", Steven S. Miller, Tobin J. Marks, and Eric Weitz, Department of Chemistry, Northwestern University, Evanston, IL 60201, USA.

12. "Nonaqueous Reductive Chemistry" W.J. Evans, S. C. Engerer, A. C. Neville and A. L. Wayda, Department of 'Chemistry, University of Chicago, Olicago, IL 60637, USA.

13. "Studies on Uranium(V) and Uranium(VI) AIkoxides: Syntheses, 13C NMR, and Magnetic Properties1t, P. Gary Eller and P.J. Vergamini, Los Alamos Scientific Laboratory, University of Claifornia, Los Alamos, New Mexico, 87545, USA.

14. "Reexamination of the Electronic structure of U(NCS)~(N(C2H5)4)4'" Edgar Soulie and Hubert Marquet-Ellis, Division de Chimie, Service de Olimie Physique, Centre DIEtudes Nucleaires De Saclay, B. P. N° 2 - 91190 - Gif Sur Yvette, France.

15. "Anionic Tetra 1'T -Allyl Complexes of Lanthanide Elements~l, S. Poggio, M. Brunelli, U. Pedretti, G. Lugli, Snamprogetti-Diris-S. Donato Milanese, Milan, Italy.

16. "Photoionization of f Electrons With UV Radiation", Russell G. Egdell, Inorganic Olemistry Department, South Parks Road, Oxford, OX! 3QR, Great Britain.

17."Magnetic Investigations on Highly Symmetric Octathiocyanato Complexes of Tetravalent ", Arno H. stollenwerk, Reinhardt Klenze, and Basil Kanellakopulos, Kernforschungszentrum Karlsruhe, Institut fiir Heisse Chemie and Fachbereich Physikalische Olemie der Universitat Heidelberg, Federal Republic of Gemany.

18. "Some NMR Spectroscopic Results on Substituted Uran.ocenes and Thorocenes A. streitwieser, Jr., Department of Chemistry, University of California, Berkeley, california 94770, USA. APPENDIX 499 19. "Non-Aqueous Olemistry of Uranium Pentafluoride", P. Gary Eller and G. W. Halstead, Los Alamos Scientific Laboratory, University of california, Los Alamos, New Mexico 87545 USA.

20. "Preparation and structure of Novel Uranium-Organyls, (,,5_C5H5)3U(IV)XL, with Trigonal-Bipyramidal Coordination", E. Klahne,J.. Kopf and R. D. Fischer, Institut ffir Anorganische und Angewandte Olemie der Universitat Hamburg, Martin-Luther-King-Platz 6, D-2000 Hamburg, 13, Federal Republic of Germany.

21. "structural Aspects of Organoactininide Complexes", Victor W. Day, Sara H. Vollmer and Cynthia S• .Day, Department of Chemistry, Univer- sity of Nebraska, Lincoln, Nebraska 68588, USA; Tobin J. Marks, Richard D. Ernst, William J. Kennelly, Juan M. Manriquez and Paul J. Fagan, Department of Olemistry, Northwestern University, Evanston, IL 60201, USA; and Josef Takats and Anita L. Arduini, Department of Chemistry, Univer• sity of Alberta, Edmonton, Alberta, Canada. INDEX

absorption spectra of uranocenes 167 actinide alkyls, steric crowding and thermal stability 242,243 catalysts 389 complexes, lability of 221,222 cyanides 239 ions, lieand field splitting in 221 tetraalkyls 242 tetrabenzyls 241 activation barrier for hydride exchange 347 for rotations 356 addition, oxidative 133 adducts with metal carbonyl compounds 90 adducts with metal nitrosyl compounds 90 adiabatic transitions 433 a-elimination 101,102 A1R3 385 alkylation reactions catalyzed by uranium complexes 390 alkyl lanthanide anions 241,242 alkyl lanthanide iodides 241 alkyls, actinide 113 bis(indenyl) 126 bis(pentamethylcyclopentadienyl) 117 carbon monoxide, insertion of 138 homoleptic 128 hydrogenolysis 136 metal 262,263 mono (pentamethylcyclopentadienyl) 127 protonolysis 136 thermal stability 132 thermolysis 131 tris(cyclopentadienyl) 113 tris(indenyl) 117 alkyl-~-chloro bridges 208

501 502 INDEX

alkynyl complexes 93 allyl anion, vibrational spectrum 491 complexes 93,348 compounds, vibrational spectroscopy 491 allyls, metal 262-265 Am(C5H5)3 28 annulated cycloo~tatetraenes 156 1161annulene 162 aryl lanthanide anions 242 aryls, actinide 113 bis(pentamethylcyclopentadienyl) 117 homoleptic 128 metal 262 tris(cyclopentadienyl) 113 atomic theory 37-40 attenuation of ~Hcon 350 auto ionization processes 425 availability of (depleted) uranium 379 availability of rare earths 380 axially symmetric crystal fields 349 axial symmetry 41,43,51,57,76-79

bimetallic organometallic compounds 107 Birmingham, J.M. 83 bis(allyl)uranium(IV) dialkoxides 236 dichloride 235 bis(arene)uranium compounds 237 bis(cycloheptatrienyl)(IV) dichloride 236 bis()actinide (IV) PE spectra 454 bis(cyclooctatetraene) complexes, vibrational spectroscopy 486 bis(cyclooctatetraene) 159 bis(cyclooctatetraene) 159 bis(cyclopentadienyl)actinide complexes, vibrational spectra 485 bis(cyclopentadienyl)actinide(IV) compounds, (C5H5)2AnX2 8 bis(cyclopentadienyl)lanthanide methyls 240 bis (cyclopentadienyl)uranium(IV)bis (borohydride) 233 bis(cyclopentadienyl)uranium bis(carbamates) 234 bis(dialkylamides) 233,234 dichloride 223 dichloride, disproportionation of 224 dihalides, complexes of 228 dihalides, u.v.-visible spectra of complexes 224,228,229 diphenyl 233 dithiolates 234 bis(indenyl)uranium(IV) dialkyls 235 bis(indenyl)uranium(IV) dichloride 235 INDEX 503 bis(n-allyl) complexes 445 bis(n8-cyclooctatetraene)uranium 149 bis(pentafluorophenyl) 95,105 bis(pentamethylcyclopentadienyl) actinide dialkyls 240 actinide dihalides 230 actinide dihydrides 240 bis(phenylethynyl)ytterbium 95,105 bis(I,3,S,7-tetraphenylcyclooctatetraene)uranium 158 bis(2,3,S,6-tetrafluorophenyl)ytterbium lOS Bleaney, B. 359 Bleaney-factor 360 bond, actinide-to-carbon 113 bridged organoactinides 9 bridging benzyne 183 bromocyclooctatetraene ISS bulky alkyl groups, complexes with 97 butadiene lanthanide compounds 237

Cade t, L. D. 8 I Cahours, A. 81 carbene complex 134 carbon monoxide, migratory insertion 138 carbonyl complexes 445 catalytic act~v~ty in diolefin polymerization 388 catalytic aspects 381 Ce(CSHS)4 86 CF-treatments of uranocene 370 charge transfer absorption bands 285 chemical shift 338 CHISi(CH3)3 1 2 -compounds of Sc and Y 99 CH2C(CH3)3-compounds of Sc and Y 99 CH2Si(CH3)2C6H4-o-0CH3-compounds of Sc and Y 99 CH2Si(CH3)3-compounds of Sc and Y 99 CH2Si(CH3)3 ligand 97 (CSHS) 2MBH4 88 (CSHS)2U(BH4)2 347 I (CSHS)2Y(CH3)2AI(CH3)21 lOS (CSHS)3An .CNC 6HI I 30 (CSHS)3EuCNC6HII' variable-temperature PMR 361 (CSHS) 3Ln.CNC6HII 28 (CSHS)3LnCNC6HII 350 5M INMX

(CSHS)3Np 27 (CSHS)3Np.CNC6HII 27 (CSHS)3Np.3THF 27 (CSHS)3MBH4 347 (CSHS)3PrCNC6HII 90 (CSHS)3UBH4 364 (CSHS)3UH 34S (CSHS)3UH3R 347 I (CSHS)3U(H20)21+-cation 343 (CSHS)3UNCS.CH3CN 343 (CSHS)3UOR 3S4 (CSHS)3UR-systems, NMR studies 34S (CSHS)3UX-systems 17 {(CSHS)3UXy}±n -systems 343 (CSHS)nMR-systems 96 (CSHS)nUIVXm 341 IC8H7P(t-C4H9)212U 3SS (CSH7Si(CH3)3)2U 369 (C9H7)nMR2-systems 96 coalescence temperature 3S2 complexes of the type LiLn(allyl)4 388 contact term 340 coordinately saturated 161 correlation energy 433 Coulomb interaction 40,47,69-71 coupling, vibrational 471,474 covalence model 314,323-32S,328-331 covalent bonding 64,2SI,2S4,267 cracking of petroleum 381 Crease, A.E. 34S crystal field 41-46,SI-60,64-68,72-7S,76-79,311,317,319,320, 321,323,324,326 crystal field splitting pattern 3S8 crystal structure of I {Yb(n-CSHS)2Me}21 208 Curie-Weiss behaviour 363 Curie-Weiss law 361 cyclooctatetraene cerium(IV) compounds 236 complexes 269,270,272,273,27S 237 INDEX 505 cyclooctatetraenes, NMR spectra 169 cyclooctatetraenide dianion, vibrational spectrum 486 cyclooctatetraenyl complexes 90 cyclooctatriene, deprotonation of 153 cyclooctatrienyne 155,159,160 cyclopentadiene, vibrational spectrum 472,473 cyclopentadienide anion, vibrational spectrum 473 cyclopentadienides 113,117,127,252,253,256-258,260-262,264-266, 274 cyclopentadienyl acetylacetonated uranium(IV) complexes, u.v.-visible spectra of 231,232 actinide alkyls and aryls 239 actinides lability of 222 cerium(IV) complexes 235 complexes 447 compounds of the actinide elements compounds of the tetravalent actinides 5 compounds of the trivalent actinides 10 compounds, vibrational spectra 473 lanthanide alkyl aluminium complexes 240 lanthanide alkyls and aryls 239 , lability of 222 (pyrazol-l-yl)borato uranium(IV) complexes, u.v.-visible spectra of 231,233 trichloride, complexes of 224 uranium trichloride, structures of complexes of 226,227 uranium trihalides, u.v.-visible spectra of complexes of 224, 225,229 uranium trihalides, complexes of 223,224 degeneracy 42,77-79 deuterated indene, vibrational spectra 480 deviations from axial symetry 356 dialkylcuprate reagents 155 diamagnetic standard 341 diastereotopic splitting by paramagnetism 358 diastereotopy 357 dicycloheptatrienylcerium(IV) dichloride 91 dicyclopentadienyl lanthanide alkoxylates 87 amides 87 chlorides 86 cyanides 87 di-tert-butyl phosphines 87 iodides 87 methoxides 87 phenoxides 87 dicyclopentadienyl yttrium chloride 105 di(methylcyclopentadienyl)lanthanide chlorides 86 506 INDEX di-n-cyclopentadienylmetal(III) methyls (M = Y,Dy,Ho,Er,Tm, or Yb) 200 di-n-cyclopentadienylmetal(III) tetraalkylaluminates 181 dipolar term ~Hdip 359 dipolar (pseudocontact) shift 313,317,318,321,323,329-332 dipole interaction 312,316,318,323,328,329 Dirac delta function 312 direct monitoring of chemical reactions by NMR 344 direct spin de localization 372 direct transfer of free spin density 355 1,1'-disubstituted uranocenes, NMR 170 di-t-butylcycloocta~etraene 151 donor-acceptor complexes 89 donor complexes 256,274 doubly-bridged species (~-halogeno-~-~lkyl) 183 dysprosium(III) 327,328,330

Edelstein, N. 370 electrochemical oxidation of uranocene 160 electronic structure 37-79,358 electronic transitions, electric dipole theory 283,299 electronic transitions, f-d 283 electronic transitions, f-f 283 electronic trans1t10ns,magnetic dipole, theory 294,299 electron-deficient alkyl bridges 182 electron-deficient bonding 181 electron energy analyzers 430 electron nucleur double resonance (ENDOR) 309,314,317,326-329, electron paramagnetic resonance 41,59,60 electron spin operator 309,313,322,326 electron spin resonance (ESR) 310,317,331 electrostatic interaction 47-51,53-55,58,69-71 elimination, reductive 133 elimination, S-hydride 131 energy levels 39,49-57,69-75,76,77 energy level calculations, configuration interaction 287,288 crystal field 287,289 free-ion 286,287,289 Slater integrals 287 spin-orbit interaction 286-288 energy scale in PE spectroscopy 431 energy transfer, vapor p~ase 304 erbium(III) 325-328,330 Er(CH3)1.xTHF . 103 Er(C4H6)3 92 e.s.r. spectra 193 2 o estimates of A2 363 INDEX 507

ethyluranocene, conformations of 172 europium(11) 319,325,326 europium(111) 322,330 Evans' method (magnetic susceptibility) 337 excited state lifetimes 299,302,303

Fantucci, P. 372 f 1-ccnfiguration 41,57 5f1-configuration (2F5/2) 15 f 2-configuration 41,49-57,69-71 5f2-configuration (3H4 ) 17 3 f" . f -con ~gurat~on (3+U ,Np 4+) (4 19/2 ) 24 f 4-configuration (5 14 ) 27 5 5f -configuration (6 H5 / 2) 28 5f6-configuration (7F) 28 o Fermi contact interaction 312,316,317,323,324 ferricenium cation 367 ferrocene 149 structure 251,252 vibrational spectrum 472 final states related to ionization of 5f subshells 462 fluxional allyl complexes 347 fluxional diamagnetic tetrahydroborate 347 fluxionality of the C6H11 -moiety 352 fluxional tetrahydrobate 348 F-orbital effect 373 Frankland, E. 81 free ion 37,49,69-71 free spin density 339,361 frontier orbital theory 161 fulvalene 162

gadolinium(111) 322,325,326,328,331 geometric factor 339,350 GF matrix method 488 Gilman, H. 82 Grignard-like systems 104 von Grosse, A. 82 group 3a elements 200 group theory, application to vibrational spectroscopy 471 g value 41,59,60 gyromagnetic ratio 340

Hart, F.A. 95 S-H-elimination 99 508 INDEX hexaalkyluranium(IV) anions 242 hindered rotation 354 holmium(II) 326 holmium(III) 325-328,330 homogeneous catalysts for butadiene polymerization 383 homogeneous reactions, catalytic aspects 381 hydride, organoactinide 136 hydrocarbyl bridges 183 hydrogen exchange 347 hydrogenolysis, actinide-to-carbon sigma bonds 136 hyperconjunctive effects 365 hyperfine coupling parameter A. 372 ~ hyperfine interaction 309,311-313,316,318,322,326-328 hypersensitive transitions 297 indene, vibrational spectrum 478 indenide anion, vibrational spectroscopy 478 indenyl compounds, 13,93,117,126,254,260,262 indenyl compounds, vibrational spectroscopy 478 INDO/2 MO calculations 364 induced electric dipole transitions, transition probability 294 "inherent shift reagent" 346 intensity measures in PE spectroscopy 431 ionic bonding 257,259,267,275 ionic model 249 ionic radii 250,251,254-256,261,262,268,269,273,275 ionization potentials 164 ion states in open shell systems 435 irreducible tensor operators 320,321,333 i.r. spectra of methyl-bridged complexes 191 i.r. spectra of ISc(n-C5HS) (Me)(L)I 205 isomerization reactions w~t~ uranium complexes 390

~somer. s h'f~ t, ,;151 Eu 418 , 419 237Np 396-458 152 Sm 419 171Yb 419 isonitrile complexes, vibrational spectroscopy 483 isotropic shift 338

Jahn-Teller theorem 441 Jones, R.G. 82

Kanellakopulos, B. knock-inhibiting agents (lanthanide derivatives) 391 Koopmans' theorem 433 Kurland-McGarvey theory 371 INDEX 509

Lande interval rule 48 lanthanide alkyls, steric crowding and thermal stability 241,243 -carbon sigma bonds, 81 carbonyls 238 catalysts 387,389 complexes, lability of 221,222 contraction 87 cyanides 238,239 germanium compounds 107 Grignard analogues 201 ions, ligand field splitting in 221 metal alkyls 179 shift reagent 359 tin compounds 107 -to-element IV sigma bonds 106 -to-transition metal bonds 108 Lappert, M.F. 96,99,100,101,106,179 Legzdins, P. 345 Lewis acid 385 Lewis acidity 204 lLi(Et20)411Lu{cH2Si(CH3)3}41 101 ligand field 41-46,51-60,64-68,72-79 LiLn(C3H5)4 346 LiLulCH2Si(CH3)3121CHSi(CH3)31 102 Li{LulcH2Si(CH3)3121CHSi(CH3)31} 101 Li n NR3 +n -complexes 97 LiM(C 6H5)4 98 Li(+med)2M!CH2Si(CH3)3!4 101 lLi(+med)311M(CH3)61 103 lLi(THF)411Er(cH3)4! 103 lLi(THF)411Yb{cH«Si(CH3)3))2}3CI! 99 L-S coupling 40,47,48 luminescence spectra 299 magnetically anisotropic systems 339 magnetic anisotropy 358 anisotropy term 363 dipolar interactions 339 dipole transitions, probability 294,299 investigations '14 isotropic molecules 349 susceptibilities 168 susceptibility 41,55-57,311,318,321,332 510 INDEX magnetic susceptibility by NMR 337 magnetic susceptibility tensor 339 mass spectrum of erbium complexes 20S mass spectrum of !M(n-CSHS)2Me2AIMe2! 193 mass spectrum of ytterb~um complexes 20S Mazzei, A. 379 McConnell equation 363,372 {M!CH2Si(CH3)3! !CHSi(CH3)3!}n 100 M!CH2Si(CH3)3!3.2THF 100 M(CSHS)2 84 mechanism of polymerization 382 metal alkyls 262,263 metal allyls 262-26S metal aryls 262 metal-free aromatic radicals C H. 368 n n , structures 2S2 method of internal coordinates, in vibrational spectroscopy 476 method of local symmetry, in vibrational spectroscopy 476 methyl lanthanum compounds 82 methyl ligand 96 miscellaneous compounds 10 mixed sandwich compounds 92 !M(n-CSHS)2(~-R)2AIR2! (M = Ti,Sc,Y,Gd,Dy,Ho,Er,Tm, or Yb) 183 MO diagram 164 molecular dimers 2S7-260,274 molecular structure of bis(n3-allyl)-bis(isopropoxy)-U(IV) dimer 387 mono(cyclopentadienyl)actinide(IV) compounds, (CSHS)3UX3 9 monocyclopentadienyllanthanide dichlorides 88 Mossbauer spectroscopy, 39S-420 magnetic hyperfine interaction 400 magnetic hyperfine interaction in Np(C 8H8)2 401 quadrupole interaction 399 quadrupole interaction ~n KNp(C 8H8)2 402,403 quadrupole interaction in NpCP4 40S,406 237 relaxation time effect on Np(CSHS)3X spectra 407-410 MR3-systems 97 mutual exclusion rule, vibrational spectroscopy 486 ! (n-(C3HS)2U(OR)2!2 346 ! (nS-CSHS)2YbX!2 341 S (n -CSHS)3YbL 341 S (n -CSHS)4U 3S0,367 INDEX 511

3S4 2S6 negative anisotropy term 36S neodymium(III) 32S,327,328,330 neopentyl ligands 200 neptunium-237, decay scheme 39S,396 neptunium-237 Mossbauer spectra, isomer shift 397 isomer shift and covalency 397 isomer shift 6~ orbital shielding 397,398 neptun~um-" 237 , 237~.Np trans~t~on" " to 397 neptunium-237 organometallic compounds Mossbauer spectra 401-407 ~somer shift, and bond length in Np(C SHS)4 413 ~somer shift and covalency in Np(IV) compounds 412 ~somer shift and covalency in Np(C SHS)3+ 413,414 isomer shift and covalency in Np(C8H8)2 402 isomer shift and covalency in KNp(CSH8)2 403 isomer shifts (table) 413 KNp(CSH8)2 403 Np(CSHS)2 406 Np(CSHS)30CH(CF3)2 412 Np(CSH8)2 401 Np(CSHS)IxTHF 404 Np(C gH7)3 407 n NpCP3 Bu 410 Np(MeCSH4)3B~4 409 ~ Np(MeCSH4)30 C3H7 411 neptunocene 36S Newman projections 349 NMR-line width, affected by paramagnetism 340 NMR of scandium or yttrium compounds 188 NMR-shift reagents 337 NMR-spectroscopy 337 NMR studies, 13C_ 371

NMR stud ~es," 31 p- 371 noble gas discharge sources 429 nuclear magnetic resonance (NMR) 309,326-328 nuclear spin operator 309 octaalkyluranium(V) anions 242 512 INDEX one-electron transitions in PE spectroscopy 423 open shell transition metal complexes 449 operator-equivalent method 43,51,52,57-59,72,75 optical spectra of (C5H5)3UX-systems 344 orbital angular momentum 312 overlap integral 314

Pa(C5H5)4 16 paramagnetic 3d-metallocene systems 372 paramagnetic NMR probe 338 paramagnetic NMR shifts 309,311,315 paramagnetic NMR shift-theory 315-317 (pentaalkylcyclopentadienyl) actinide halides 230 (pentaalkylcyclopentadienyl) actinide trichlorides, U.v. -visible spectra of complexes 230 pentafluorophenyl ligand 107 pentalene 162 pentamethylcyclopentadienyl actinide complexes, vibrational spectra 476 permethylation of C5H5 rings 341 PE spectroscopy 421 photoelectron cross-sections 441 photoeleetron spectrum (PES) of thorocene 164 photoelectron spectrum (PES) of uranocene 164 photoinduced S-hydride elimination 117,126 photolytic cycloaddition 155 plutonocene 57 polarization model 313,322,323,328-331 polymerization of a -olefins 389 praseodymium(III) 325-328,330 preparation in aqueous solutions 5 preparation in solution 2 preparation in the melt 3 PriGe(C6F5)3i3 107 promethium(III) 330 protonolysis, actinide-to-carbon bonds 136 proton-proton coupling 350 PR2-substituted uranocene 357 pseudo contact (dipolar) shift 313,317,318,321,323,329-332 pseudohomogeneous reactions, catalytic aspects 381 2 o quadratic CF - parameter A2 367 Racah parameters 48 radial charge density 37,38 radial parameters 46,48,57,69-71 radial wavefunctions 44 INDEX 513

reactions of uranocenes 156 reactions of !{Y(n-C5H5)2Me}2! with aluminium alkyls 207 reactions of !{Y(n-C5H5)2Me}2! with Lewis bases 207 reduced matrix elements 49,73-75 relation between PE spectroscopy snd other electronic spectroscopy techniques 427 relaxation energy 433 relaxation time TIe 310,311,315,316 Rieche, A. 81 Rice, W. W. 82 rocking frequencies 191 rotation about the P-C(butyl) bond 355 rotation about U-C-a bonds 349 5 rotation of an unsubstituted n -C5H5 ligand 346 Russell-Saunders coupling 40,47,48

(III) 319,322,330 sandwich compounds, vibrational spectra 473,477 scandium phenylacetylide 94 SC!CH2C6H4N(CH3)2!3 98 Sc!CH3Si(CH3)2C6H40CH3!3 99 Sc(C5H5) 3 253 SCF-Xa scattered wave calculations 16S Schumann, H. 81 second-order Zeeman contribution 368 second-order Zeeman (SOZ) effect 317,324 second-order Zeeman interactions 373 separation of 6Hcon and 6Hdip 348 separation of 6Hdip from 6Hcon 358 separation of 6Hdip and 6Hcon 358 shake up and shake off processes 423 shift reagent technique 349 sigma bonds, actinide-to-carbon 113 Np(C5H5)3' BH4 bond 413 NpCI 3 , C5HS bond 414 Np(CSHS)3' n-butyl bond 414 Np(C SH5)3' OR bonds 411 Np(CSHS)3' phenyl bond 414 thorium-to-carbon 113 uranium-to-carbon 113 con s~gn. 0 f LlAH 340 514 INDEX

sign of (XII-X.l) 366 2 simultaneous diagonalization of the 5f ground configuration 370 skeletal modes 191 Slater integrals 47-49 Slater parameters 49,51,58 Sm(C5H5)3 253,260 sodium naphthalide 154 special preparation methods 3 spectra, absorption, Gd(C5H5)3 284 La(C5H5)3 284 Nd(C5H5)3 282 Pu(C5H5)3 293 Spiegl, A.W. 367 spin delocalization mechanism 340 spin delocalization term 340 spin density 313,340 distribution 371 spin Hamiltonian 59,60 spin-orbit coupling 439 spin-orbit interaction 40,45-50,58,63-68,311,323 spin polarization 372 spin transfer 351 static magnetic susceptibility 344 stereospecific polymerization 381 steric congestion 348 Stevens-parameter ~JlaIJ> 368 strong ligand field limit 51,76-79 structure of IYb(n-C5H5)2Me2AIMe2I 193 substituted uranocenes 153-155 systems of the type (CH3C5H4)3UX 366

Tanabe-Sugano diagrams 53-55 t-C4H9 ligand 97 temperature dependance of ~Hiso 341,342 temperature expansion 318-321,324 temperature independant ~Hcon 361 tensor operator 48,58,59,73-75 (III) 325-328 tetraalkyluranium(IV)-systems 345 tetra(allyl)uranium 346 tetrafluorenyl cerium(IV) 91,236 tetrahydroborate complexes, vibrational spectra 484 tetrakis(cyclopentadienyl)actinide complexes, vibrational spectra 474 INDEX 515

tetrakis(cyclopentadienyl) compounds, An(CSHS)4 S tetrakis(2,6-dimethylphenyl)lutetiate anion 98 1,3,S,7-tetramethylcyclooctatetraene IS3 1,3,S,7-tetra-t-butylcyclooctatetraene 164 Th(CSHS)3 IS thermal stability, actinide-to-carbon sigma bonds 132 thermolysis, organoactinide 131 thorium alkyls 113 thorium aryls 113 thorium-to-carbon sigma bonds 113 thorocene 164 thorocene, photoelectron spectrum (PES) of 164

t h orocenes, 13C magnetIc' resonance spectra 0 f 168 thorocenes, NMR spectra 169 thulium (II) in CaF7. 314,32S,326 thulium (III) 32S,330 time-averaged crystal field 367 transition probabilities 291 trialkyl lanthanides 241 tricyclopentadienylcerium(IV) chloride 89 tricyclopentadienyl complexes 83 tricyclopentadienyl lanthanides 83 tricyclopentadienylscandium 84 triethylscandium 82 triethylyttrium 82 trimethylmethylenephosphorane 104 trimethylsilyl ligands 200 triphenylscandium 9S tris-allyl-uranium halides 383 trislbiS(trimethYlSilYl)-amidOlneOdymium 107 tris bis(trimethylsilyl)-amido praseodymium 107 tris(cyclopentadienyl)actinide alkyls, alkyl exchange 241 tris(cyclopentadienyl)actinide complexes, vibrational spectra 474 tris(cyclopentadienyl)actinide(IV) compounds, (CSHS)3AnX 6 tris(cyclopentadienyl)actinide(IV) PE spectra 456 tris(cyclopentadienyl)lanthanide complexes, vibrational spectra 476 tris(cyclopentadienyl)thorium(III) compounds 240 tris(cyclopentadienyl)uranium chloride, u.v.- visible spectrum 223-22S tris(cyclopentadienyl)uranium chloride, vibrational spectrum 471 tris(indenyl)actinide complexes, vibrational spectra 478 tris(indenyl)actinide(IV) PE spectra 461 unusual NMR of (CSHS)3UF 343 uranium alkoxides 38S 516 INDEX

alkyls 113 aryls 113 carbonyls 237,238 catalysts 381 (IV) compounds, U(C5H5)4 17 reforming catalysts 381 -to-carbon sigma bonds 113 trifluoromethyls 242 uranocene 51,55-57,91,149,269,270,272,273,275,367,368 uranocene, bonding in 164 d and f orbitals in 165 derivatives 354,367 electrochemical oxidation of 160 hydrogenation of 160 ionization potentials of 166 metalation of 159 photoelectron spectrum (PES) of 164 preparation of 149,154 reactions of 159 reaction with nitro compounds 160 reduction of 164 ring-metal covalency in 158 ligand exchange of 158 paramagnetism and NMR spectra of 168 substituted 151,152 visible spectra of 166 -type molecules 41,43,57 variable temperature 13 C NMR of yttrium complexes 191 vertical ionization energy 433 vibrational fine structure 437 vibrational spectroscopy 467 vibronic transitions 285

Wilkinson, G. 83 Wolfsberg-Helmholz approximation 57,58

X-ray diffraction 249,252,266 X-ray sources 430 X-ray study of (C5H5)3PrCNC6H11 351

!Yb{CH(SiMe3)2}3C1! 199 !Yb(n-C5H5)2Me2AIMe2! 199 Y {CH!Si(CH3)3!2}3 99 ylide complexes 104 !Y(n-C5H5)2A1Me3c1! 208 INDEX 517

I {Y(-CSHS)2Me}21 , 13C NMR of 20S I {Y(-CSHS)2Me}21 , PMR spectrum 204 ytterbium (III) 32S,328,329 ytterbium (III) in CaF2 314,324-326 yttrium-carbon coupling 191

Zeeman interaction 41 Ziegler-Natta catalysis, intermediates in 183