559 Acidic Substrates Deprotonation – F-Element–Metal

559

Index

a C–C bond formation reactions 301, 302 acidic substrates deprotonation chalcogenide clusters 97Â–99 – f-element–metal complexes 60 chromium 139–141 – oligomerization 60, 61 cluster compounds adduct formation – classes 485 – Coulomb attraction, ionic species 57 –Zintlcompounds,see Zintl compounds – and ligand rearrangement, Fe/Yb system 59 cobalt – [MCp*] (M = Al, Ga) and f-element moieties 58 – Co(I) and Co(II) oxidation 279 –RE–Snbonds 59 – Co–Co bond length 279 alkane and amine elimination – dicobalt compounds, see dicobalt compounds – CH-activation, coligand periphery 54 – doublet and quartet spin states 284 –[Cp3USnPh3]preparation 53 – extended metal-atom chains (EMACs) 282 – homogeneous reaction behaviour 51 – Hückel molecular orbital method 284 –RE–Rebonds 53 – intermolecular interactions 283 –U–Rebonds 54 – LUMO 284 alkane elimination 466 – polymorphism 283 allylic and benzylic oxidations 301 – tri- and penta-nuclear cobalt 284 amido, imido and nitride complexes 92, 93, 95 complete active space self consistent ﬁeld (CASSCF) 2 b complexes BIAN, see 1,2-diiminoacenaphthenes (BIAN) – with actinide metals 69 bimetallic compounds – with rare earth metals 66 – dinickel compounds, see dinickel compounds conductive atomic force microscopy (CAFM) 13 – dipalladium, see dipalladium compounds copper(I)–copper(I) interactions – diplatinum, see diplatinum compounds – ab initio investigation 399 – heterobimetallic, see heterobimetallic compounds – acetonitrile and cuprophilic interaction 401 – metal–metal bonds 325 – carbanion-bridged systems 400 borylene bridging dimanganese(I) complexes 178, – copper–copper bond order 402 179 – Cu–Cu distances 398 bridging/terminal Pn atoms – cyclic trimer 402 – cationic complexes 548 – dicopper complexes 401 – 92 and 94 core structures 548, 549 – gold(I)–gold(I) interactions, see gold(I)–gold(I) interactions c – Hückel calculations 398 CAFM, see conductive atomic force microscopy – hydride bridges 400 (CAFM) – hydrogen bonding 403 carbene bridging dimanganese(I) complexes 178 – linear geometry 401 carboxylate 250, 252 – lithium 402 CASSCF, see complete active space self consistent ﬁeld – metal–metal bonding 400 (CASSCF) – silver(I)–silver(I) interactions, see silver(I)–silver(I) catecholates 248, 249 interactions

Molecular Metal-Metal Bonds: Compounds, Synthesis, Properties, First Edition. Edited by Stephen T. Liddle. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA. 560 Index

copper(I)–copper(I) interactions (contd.) – arenes 330 – tetrameric (trimethylsilyl)methyl copper 398 – with aryl and aryne ligands 335–337 – triazenido ligands 398 – bis(phosphane) ligands 338 covalent metal–metal bonding – bisdentate monoanionic carboxylates 328 – Figgis/Martin scheme 415 – bridging ligands 330 – gold–gold bonding, see gold–gold bonding – H-migration mechanism 332 – mixed-valent copper(I)/copper(II) complexes 415, – LiN(SiMe3)2 338 417 – mechanism 330, 331 – paddlewheel complexes of copper(II) 415 – mediated hydrodesulfurization 338, 339 – silver–silver bonding 418, 419 – molecular hinge, Ni(I)–Ni(I) bond 332, 334 cyclo-organobismuthines 524 – monoanionic pyrrole-based PNP pincer cyclo-organostibines ligand 340 – dehalogenation, organoantimony dihalides 523 – monoatomic bridged Ni(I)–Ni(I) bond 338 – description 523 – μ-iodide μ-nitrosyl compound 339 – molecular and supramolecular structure 524, 525 – multidentate N,P-donor ligands 339 – solid state structure 523 – N-heterocyclic carbene (NHC) ligand 338 – supramolecular structure 524 – Ni(I)–Ni(I) bond lengths 329 – N,N ′-trimethylsilyl-phenylamidinate ligand 328 d – salt elimination 332 DAD, see 1,4-diazadienes (DAD) ligands – stepwise reduction, Ni(II) dibromide 335, 336 d-block-group 13 464 – syn-η2:η2-bonding model 330, 332 – alkane elimination 466 dinickel(II) compounds – anionic gallium analogues 465 – carbene ligand (RR′C2−) 344 – diyl systems 465 –closed-shelld8 electronic conﬁguration 340 – metal-mediated dehydrogenation 465 – imide (AdN2−) bridging 342 – organometallic complexes 465 – μ-methylene compound 344 – oxidative addition vs. adduct formation 466, 467 – μ-Nimide bridging compounds 342 – salt elimination 465, 466 – Ni(II)–Ni(II) bond lengths 342, 344 density functional theory (DFT) 3 – paddlewheel 341 1,4-diazadienes (DAD) ligands 51 dinickel(III) compounds 344, 345 dicobalt compounds 279 dipalladium compounds – antiferromagnetic interactions 281 – description 347 – dicobalt paddlewheel compounds 280 – dipalladium, see dipalladium(0) compounds – magnetic communication 282 – dipalladium(I), see dipalladium(I) compounds – N-donor bridging ligands 280 – dipalladium(II), see dipalladium(II) compounds – one-electron oxidation 281 – dipalladium(III), see dipalladium(III) compounds – tetragonal species 280 – mixed-valent 370 1,2-diiminoacenaphthenes (BIAN) 51, 52 dipalladium(0) compounds diiron – aluminium(I) ligand 348 – Fe–Fe bonding 233, 235, 236 – μ-P, P′-coordinated diphosphane ligands 348 – planar paddlewheel complex 231 – Pd(0)–Pd(0) bond lengths 348 – tetragonal complexes 226, 227 – steric bulky Ga(I) ligand [GaCp∗Ph] 347 – trigonal paddlewheel complexes 228Â–231 dipalladium(I) compounds dimeric magnesium(I) compounds 30, 31 – allyl bridging and insertion of CO2 360, 361 dinickel compounds 326 – bis-NHC ligand 362 – dinickel(0), see dinickel(0) compounds – chiral ligand 358 – dinickel(I), see dinickel(I) compounds – ‘corner- and edge-sharing’ 349, 350 – dinickel(II), see dinickel(II) compounds – gallium(III) halide 358 – dinickel(III) 344, 345 – with mono-bridging-atom ligand 354 – mixed-valent 345, 346 – neutral arene, anionic allyl/cyclopentadiene ligands dinickel(0) compounds 358 – Ni(0)–Ni(0) bond lengths 326, 327 – NPN-tridentate ligands 360 – oleﬁn ligands 326 – paddlewheel compounds, see paddlewheel dinickel(I) compounds compounds – α-diimine 335 – Pd(I)–Pd(I) bond lengths 351, 362 – anionic NHC ligand 339 – Pd-phenyl interactions 358 – antiferromagnetic coupling 329 – pyrrole-based PNP pincer ligand 361 Index 561

– redox non-innocent ligands 362 – description 379 – triene-bridging dipalladium(I) sandwich compounds – ortho-C–H bond of phenol 380 359, 360 – paddlewheel 382, 383 – with unsupported Pd(I)–Pd(I) bond 349, 350, 352, – Pt(III)–Pt(III) bond lengths 381 353 – Pt(III)–Pt(III) compounds 198 and 199 380 dipalladium(II) compounds – Pt(IV) trimethyl compound, C6 D6 solution 380, – with 2-arylpyridine ligand 363, 364 381 – benzylidenic C=C double bond 364 dirhodium complexes – bis(pentalene) compound 144 364, 366 – carboxylate-containing residues 305 – catalytic functionalization, C–H bond 363 – catalytic cycle 303 8 – d electron conﬁguration 363 – excited-state photophysical properties 304 – paddlewheel compounds 364, 365 – as hosts 305, 306 – Pd(II)–Pd(II) bis-(monoanionic-allyl) compound – multielectron transfer reactions 303 366 – multimetallic assemblies 310, 312, 314 dipalladium(III) compounds – π-arene interactions 306, 307 – catalytic C–H bond acetoxylation 367, 368 – π-backbonding 308, 309 – C–Cl bond 367 diruthenium – 146 147 compunds 366 – metal–metal bonds 237 – 155-156 compounds 368 – paddlewheel, see paddlewheels – as intermediate for Pd(II)/Pd(IV) oxidation. 367, distibines and dibismuthines 519 369 – examples of reactions 520, 521 – Pd(III)–Pd(III) bond lengths 367 – Pn–Pn bond formation 520 – UV–vis spectroscopy 367, 369 – secondary 520 diplatinum compounds – structures 520, 522 – description 370 dorbitals – diplatinum(0), see diplatinum(0) compounds – bends and stretches, Ru (dpa) X and Cr (dpa) X – diplatinum(I), see diplatinum(I) compounds 3 4 2 3 4 2 12, 13 – diplatinum(II), see diplatinum(II) compounds – dirhodium carbene complex Rh (HCOO) (CH ) – diplatinum(III), see diplatinum(III) compounds 2 4 2 10, 11, 12 – metal–metal bonded moieties 371 – electron–electron repulsions 7 – mixed-valent 382–384 –Fe(CO) 15, 16 diplatinum(0) compounds 2 9 – iconic quadruple bond [Re Cl ]2− 7, 8 – 160-163 compounds 371 2 8 – naked transition metal diatomics 6 – kinetical stabilisation 371 3− – Pt(0)–Pt(0) bond lengths 372 –[Ru2Cl9] ,M2X9 family 14 σ – series of 371, 372 – bonding 9 diplatinum(I) compounds 371 – singlet ground state, sextuply bonded W2 6 – spherically symmetric 3d cores 7 –BrønstedacidCF3 SO3 H 372, 373 – comproportionation reaction 374 – ‘supported’ and ‘unsupported’ bonds 5 –C(sp1)–P bond 372, 374 – ultrashort Cr–Cr quintuple bonds 9, 10 – diphosphane bridging 375 double-bonded species – diplatinum(I) hydride 376 – dipnictenes structure 530 – E–H bond activated products 376 – selected structural data 530, 531 – phosphide bridged, bis-ethylene compound 166 – 33 structure 529 371, 372 – 35 structure 530, 532 − – 34-Tbt and [34-Bbt]•− structure 530, 531 – phosphinito (R2PO ) bridging 374 – Pt(I)–Pt(I) bond lengths 373 double bonds (E=E) diplatinum(II) compounds – cyclic silylenes 496 – 194 compound 376, 379 – description 494 – description 376 – distannanes bonding 38, 494, 495 – hydride- and acetylide-bridging compounds 376, – reﬁned bonding model 495 378 – sila-butadienes 496 – hydride bridged Pt(II)–Pt(II) bond 379 – Si=Si and Ge=Ge bonds reactivity 497 – macrocyclic N2 S2 ligand 376, 378 – trans-bent structure, 38 [R=CH(SiMe3)2] 494 t – Pt(II)–Pt(II) bond lengths 378 – trialkylsilyl derivative [( BuMe2Si)2Sn]2 495 diplatinum(III) compounds double bonds (Tm=E) 508, 509 – 206 and 207 compounds 381, 382 double salt elimination 468 562 Index

e f-element–TM bond formation 48 early-late heterobimetallic complexes – early salt elimination reactions 49 – Bader surfaces 77 – forming An–TM bonds 49, 50 – carbonyl metalate derivative 75 – forming RE–TM bonds 49, 50 – electronegativities 75 – limitations 49 – metal–metal bond polarity 75 Fe–M heterometallics – Ti–Co bonds 76 – Fe–group 4 heterometallics 258, 259 –Ti–MandZr–Mcomplexes 75 – Fe–(group 5–7) heterometallics 260–263 – triarylphosphine ligand 76 – Fe–group 9 heterometallics 263, 264 – Zr–Ru bonding 76 – Fe–group 10 heterometallics 264, 265 early-late heterodinuclear complexes 81 – Fe–group 11 heterometallics 265, 266 – cooperative reactivity 82 forbitals –insertions,see insertions polar metal–metal bonds –C60 17, 18 – phosphinoamide-bridged Zr–Co, see –description 16 phosphinoamide-bridged Zr–Co – orbitals occupations, U2 (CASSCF) 17 electronic and magnetic materials 240, 241 – trans bending, distannenes and distannynes 17, electronic coupling 18, 19 – anthracenyl bridge 146 formamidinate 252 – bandwidth 150 formation of C–N bonds – classiﬁcation 146 – bimetallic framework 299 – compounds 147 – C–H amination reaction 298 – delocalized mixed valence ions 147 – dirhodium carboxamidates 298 – dimers of dimers 150 – intramolecular amination 298 – dinuclear complexes 146 – intramolecular selectivity 299 – frontier molecular orbital energy 145 – X-ray crystallography 300 – IVCT band 148 functionalization of C–H bonds – lanthanide contraction 146 – catalytic performance evaluation 293 – mixed valence systems 149 – diazo compounds 294 – MM quadruply bonded systems 150 – diazo insertion 294 – NIR electronic absorption spectra 149 – dipolar cycloaddition reactions 296 – orbital energies and metal–ligand 146 – dirhodium catalysts 293 – resonance electronic transitions 149 – indole derivatives 293 – single cyclic voltammetric wave 146 – metal-catalyzed cycloadditions 294 – terephthalate 147 – orthometalated aryl phosphines 297 – voltammograms 147 – oxonium 296 – X-band EPR spectra 148 functionalization of Si–H and S–H bonds 300, 301 extended metal-atom chains (EMACs) 13 g f G12 and transition metals f-block-group 476, 477 – AACVD 441 f-block metal–group 14 bonds – Au(I) metallocryptand cage 449 – group 14–lanthanide and actinide bonded – Cd–Ni distances 446 compounds 504, 505 – Cu–Hg bond 448 – insertion reaction of 101 with ArHC 505, 506 – G12–Fe and G12–Ru 445 – 97 reaction with PhSiH3 505, 506 – Hg–Ag-bonded compound 448 Fe–Fe bonding – Hg–Mn-bonded complexes 443 – hexaamide ligands 234 – iron and mercury 444 – hexaamide ligands multi-electron processes 235 –Li[Cp2 MSnPh3] 442 – hexanuclear Fe6 235 – Nb(II) radicals 442 – hydrocarbon-supported 236 – Pd–Zn bonded compound 447 – intermetallic carbide clusters 236 – P,N-type bidentate donors 444 – Mössbauer doublets 234 – Pt-Cd bonded complexes 446 Fe-group 4 bonding in clusters 259 – sodium amalgam 443 f-element–MM bond formation – TM–ZnR complex 444 – BIAN ligands 51, 52 – Vaska’s complex 445 – DAD ligands 51, 52 [G12–G12]2+ ions – ytterbium–tin bonds 51 – dicadmium(I) and dizinc(I) salts 430 Index 563

– reactivity 434 group 6 metal–metal bonds – synthesis and structure 430, 431 – chromium 139–141 gold–gold bonding – electronic coupling, see electronic coupling – semi-/fully supported 419 – molecular assemblies 143Â–145 – unsupported gold–gold bonds 420, 421 – molybdenum and tungsten 141 gold(I)–gold(I) interactions 406 – parallelepiped compounds 139 – aurophilic interaction 407 – photophysical studies, see photophysical studies – diauration at hydrogen 407 – quintuple bonds, see quintuple bonds – geminal auration at carbon 407, 409 group 8 meta–metal bonds – luminescent complexes 410, 411 – cognization 225 – photocatalysis 412 – homobimetallics, see homobimetallics – redox reactions 409, 410 group 12 metal–metal bonds – thin-ﬁlm deposition 411 – dicadmium(I) salt 429 group 1 bimetallics – heterobimetallics, see heterobimetallics – homodiatomics and heterodiatomics 23, 24 – homobimetallics, see homobimetallics –L:→M–M species 24 group 13 metal–metal bonds –Li2 and Na2 24 – d-block-group 13, see d-block-group 13 – stable complexes with group 1 25 – f-block-group 476, 477 – stable metal–metal bonded complexes 25Â–27 – p-block 458 group 2 heterobimetallics – ‘renaissance’ 455 –description 34 – s-block 455 –group2–TM,see group 2–transitional metal group 2–transitional metal complexes complexes – AIM analysis 38 t group 8 heterobimetallics – Ar = Dip, R = SiMe Bu2 34, 36, 37 –intertriadM2 complexes, see intertriad M2 – Be–Pt distances 34 complexes – {Co} = Co(CO)2(PCy3) 34, 35 –intratriadM2 complexes 257 – heterobimetallic complexes with tolylcarbodiimide group 2 homobimetallics 38 –description 27 – hydride complex, [Cp*Ir(PMe3)(H)(μ-MgPh)]2 37 – diatomics and species 27, 28 –Mg–Modistances 34 – isolable group, see isolable group 2 metal(I)–metal(I) – short intermetal distances 38 bonded dimers – Sr–Co bonding 38 – transient group 2 metal(I)–metal(I) bonded dimers guanidinate 252 29 group 2–main group metal complexes h –Ar=Dip 39 halide 253 – axial THF ligands 40 halide abstraction 469, 470 – Ca–Ga dissociation energy 41 heteroatomic metal–metal bonds – Ca–Sn distances 40 – f-block metal–group 14 bonds, see f-block – Mg–Ge interactions 40 metal–group 14 bonds –[Mg{Ge(SiMe3)3}2 (THF)2]structure 40 – p-block, see p-block metal–group 14 bonds – trigonal bipyramidal geometry with gallyl ligands – s-block, see s-block metal–group 14 metal bonds 41 – transition, see transition metal–group 14 bonds group 1 metal complexes 456 heterobimetallic complexes 421–423, 74 group 2 metal complexes 457, 458 – metal–metal bond polarity 75 group 12 metal complexes 458, 459 – synthetic strategies, see synthetic strategies group 14 metal complexes 464 – Ti/Zr/Hf–M heterodimetallic complexes 79–81 group 4 meta–metal bonds heterobimetallic compounds – degradative reaction 73 – with [Ag(ClO4)PPh3] 385, 387 – early-late heterodinuclear complexes, see early-late – description 384 heterodinuclear complexes – ‘dimer-of-dimer’ 386, 389 – heterobimetallic complexes, see heterobimetallic – gallium(I) ligand bridged 385, 388 complexes – heterobi-/multi-metallic Pt–Pd compounds 384, – as potential catalysts 85 385 group 5 metal–metal bonds –M–M′ bond lengths 386 – inorganic and organometallic chemistry 91 – Pt(II) disilyl and [Pd(PEt3)4] reactions 384 – vanadium complexes, see vanadium complexes – Pt(II)–Ni(II) compound 216 384, 385 564 Index

2+ 2+ heterobimetallic compounds (contd.) –withMn2 core complexes, see Mn2 core – sterically demanding phosphine 386, 388 complexes 3+ heterobimetallics –withMn2 core complexes 176–178 4+ – G12 and transition metals, see G12 and transition –withMn2 core complexes 175–177 metals – Mn–Mn bonding species 175 – G12–G13 bonds 437, 439 metal–antimony bonds – G12–G14 bonds 439, 440 – cationic palladium complex 97+ 550 – G12–G15 bonds 440 – crystal structure of 98 550 homoatomic group 14–group 14 bonds – crystal structure of 99 551 – cluster compounds, see cluster compounds – description 549 – double bonds (E=E), see double bonds (E=E) – group 6 and 8 complexes 549 – single bonds (E–E), see single bonds (E–E) – molybdenum complex 95 549 –triplebonds(E≡E), see triple bonds (E≡E) – stiboranyl complexes derivative 98, 550 homobimetallics 225 metallophilic interactions involving gold(III) 414 – diiron 226 metal–metal bond oxidation – diruthenium, see diruthenium – bond disruption enthalpies, uranium complexes – G12–G12 bonded complexes, see molecular 62, 63 G12–G12 bonded complexes –description 62 – reactivity and catalysis 242, 243, 245 metal–metal bonds – synthesis and structures 430, 431 – arbitrary metal centres 1, 2 homodinuclear group 4 complexes 73, 74 –DFT 3 – discrete molecular systems 1 i –dorbitals,see dorbitals icosahedral [Al13]–cluster 4, 5 –forbitals,see forbitals insertions polar metal–metal bonds 82, 84 –ns orbitals, see ns orbitals intertriad M2 complexes 258 –porbitals,see porbitals intramolecular deprotonation and C–H activation – radial distribution functions 1, 2 – cluster formation RE–Re complexes 61, 62 metal-only Lewis pairs – polyhydride Lu–TM clusters formation 63 – Group 13 elements 467 iridium – neutral and zwitterionic forms 468 – small molecule and bond activation 316, 317 – zwitterionic form 467 – synthesis and characterization 315, 316 MI heterocycles isocarbonyl problem 48 – anionic gallium heterocycle 475 isolable group 2 metal(I)–metal(I) bonded dimers – coordination sphere 474 – dimeric magnesium(I) compounds 30, 31 – heterocycle plane 474 – dimeric magnesium(I) compounds structure and – metal-halide bonds 475 bonding 32 – monomeric heterocycles 473 – bulky ligands (R) into dimers 29 – σ-gallane complex 475 – low-valent Mg complexes 31 – transition metal carbonyls 476 – magnesium(I) dimers synthesis 29, 30 MI species –Ncenters,β-diketiminate ligands 29 – heterocycles 471 – reactivity 32, 33 – ligand displacement reactions, see ligand – structure and bonding 31, 32 displacement reactions – M–X and M–M bonds 471 l mixed-valent dinickel compounds ligand displacement reactions – NHC-coordinated dinickel(0) compound 346 (n+m)+ – Fe–Al bond length 472 –Ni2 345 – Group 13 diyls 471 – Ni–Ni bond lengths 346 – homoleptic complexes 473 – Ni(II)–Ni(0) compounds 345Â–347 – monomeric state 471 mixed-valent dipalladium compounds 5+ – M–X bonds 473 –Pd2 compound 159 370 – terphenyl indium diyl 472 – Pd–Pd bond lengths 370 – Pd(II)–Pd(0) interaction 370 m mixed-valent diplatinum compounds magnesium(I) dimers synthesis 29, 30 – 212-214 compounds 382, 384 manganese – Pt–Pt bond lengths 383 0 –Mn2 core complexes 183, 185 – synergistic 2-centre oxidation 382, 383 Index 565

– triplatinum compound 215 383, 384 –Re2(tbn)4Cl2 and Re2(tbo)4Cl2 211 0 Mn2 core complexes 183, 185 – structural data 208, 215 2+ Mn2 core complexes noncovalent metal–metal interactions – with carbene/borylene bridging ligands 177–179 – “aurophilicity” 397 – with chalcogenide and bridging ligands – closed-shell attractions 397 181–184 – copper(I)–copper(I) interactions, see – with unsupported Mn–Mn bonds 178, 179, copper(I)–copper(I) interactions 180, 182 non-paddlewheel Fe2 complexes 3+ Mn2 core complexes 176–178 231, 232 4+ Mn2 core complexes 175–177 non-paddlewheel Ru2 complexes molecular G12–G12 bonded complexes – tetragonal 247, 248 – arylmetal iodide 433 ns orbitals – catalytic activity 437 – Cd–Cd bond 4 – Cp*ZnZnCp* 437 –(Cp)2 Lu(thf)-Ru(Cp)(CO)2 5 – dimercury(I) salts 434 – HOMOs 3, 4 – Hg–Hg–bonded complex 432 – ‘superhalide’ 4, 5 – ligand exchange reactions 434 – pseudo-spherical clusters 4 – nitrogen ligands 431 – Zn–Zn bonding 3 – pyrophoric compound 431 – Zintl cluster anion 433 o – Zn–Zn bond cleavage 435 (O, O) bridging ligands molecular string complexes 151 ⋅ molecules and oligomers – cis-Re2[(CH3)3CCOO]2Cl4 2DMSO and ⋅ – cyclic oligostannanes 493 Re2(HPO4)2(H2PO4)2(H2O)2 4H2O – cyclic silanes 492 209, 210 – compounds 206 – Ge–Ge bonding 492 + – low HOMO–LUMO energy gaps 491 –Re2(GABA)2Cl5(H2O) cation and Re2(esp)2Cl2 – mono- and bis-silylenes 492 207 – Pb–Pb derivatives 493 –Re2(O2C(CO)Et)Cl6− anion.Re...Clcontacts – Wurtz-type coupling 491 208, 209 molybdenum and tungsten 141Â–143 Os–group 6 heterometallics 271 M–Sb and M–Bi bonds Os–group 9 heterometallics 272 – bridging/terminal Pn atoms, see bridging/terminal oxidation state +1 Pn atoms – aggregated oligomeric species 462 – description 533 – aluminium and gallium 462 – RPn fragments, see RPn fragments – dianionic systems 463 – ligand steric proﬁle 463 –R2Pn fragments, see R2Pn fragments multimetallic sandwich compounds – M–M interactions 461 – description 387 – organometallic systems 462 – steric protection 463 –Pd3 (C7 H7)2 Cl3][PPh4]and[Pd5 – tetrahedral arrangement 462 (napthacene)(toluene)][B(3,5-(CF3)2 C6 H3)] 388, 389 – Tl-C vectors 462 – redox reactions 389 – triple bond formulation 463 +2 oxidation state n – alkoxo derivatives 460 NIR electronic absorption spectra 149, 150 – alkyl/aryl and silyl donors 459 (N, N) bridging ligands – base-stabilized systems 460 – anilopyridinate derivatives 212 – carboxylate and acetylacetonate 461 – bicyclic guanidinate complexes 211 – dimeric systems 459 – description 211 – isomeric forms 461 – electrochemical measurements 212 –MII systems 460 – electronic absorption spectra 213 – steric factors 459 –Re2(3,5-(CH3)2ap)4Cl2 and Re2(ap)4Cl2 212 – structural motifs 460 –Re2(3-Clap)4Cl2 and Re2(3,5-Cl2ap)4Cl2 212 – X-ray crystal structures 461 –Re2(DCyBA)2Cl4 and Re2(DmAniF)2Cl4 213, 214 oxidation states, less than +1 –[Re2(DMBA)4(WO4)]∞ 214, 215 – concentric shells 464 –Re2(hpp)4 F2 215 – cubane system 464 566 Index

p – intramolecular deprotonation and C–H activation, paddlewheel compounds see intramolecular deprotonation and C–H – bidentate EXE type ligand and bridging M–M bond activation 355 – metal–metal bond, see metal–metal bond oxidation 5+ – indolyl-phosphine ligand 355 Re2 core complexes 216, 217 6+ – Pd(I)–Pd(I) compounds 356 Re2 core complexes – triazenido ligands (R–NH–N=N–R′) 354 – compounds with (O, O) and (N, N) bridging ligands – tridentate ligand 356 206, 209–211 paddlewheels 237 – compounds with (N, N) bridging ligands, see (N, N) 4+ –Ru2 238 bridging ligands 5+ –Ru2 237 – compounds with no bridging ligands 205–207 6+ 7+ –Ru2 239 Re2 core complexes p-block metal–group 14 bonds – description 204 t − – (AlCl3)2[EN Bu]4, [{(Ph3Ge)3Ga}Ga] anion (73) –Re2(tbn)4Cl2+ cation and tbn anion 204, 205 t − and [( Bu2MeSi)2Ge}2In] anion (74) 502 – structural data 204, 205 8+ – Ge–Bi bonded compounds 504 Re2 core complexes 203, 204 – N-heterocyclic carbene analogue to Group 14 centre reductive cleavage, metal–metal bonds 503 – homometallic M–M bond 54 – neutral and anionic E–E′ bonded cages 502, 503 – lanthanoids Sm, Eu, and Yb into Ga–Ga bonds 56 phosphinoamide-bridged Zr–Co heterobimetallic – reactions within system activated ytterbium 55 ∗ complexes 85 –[SmCp 2] reaction with BiPh3 57 photophysical studies – [(thf)4Ln{Sn(SnMe3)3}2] (Ln = Yb, Sm) from – heteroleptic compounds 152Â–155 Me3SnCl 55 – homoleptic compounds 151, 152 – U–Co complex formation via Co–Co bonds 57 – transient absorption spectra 155 – Yb–Fe bonds formation of Fe–Fe bonds 56 –TRIR,see time-resolved infrared studies (TRIR) rhenium 8+ π-backbonding 308, 309 –complexeswithRe2 core 203, 204 planar paddlewheel complex 231 – description 202 2− Pn–Pn (Pn=Sb, Bi) multiple bonds 529 –Re2Cl8 anion 202, 203 4+ – double-bonded species, see double-bonded species –Re2 core complexes 216, 218–220 5+ 5+ – triple-bonded species, see triple-bonded species –Re2 core complexes, see Re2 core complexes 6+ 6+ polymers –Re2 core complexes, see Re2 core complexes 7+ 7+ – backbone, group 14 polymers 493 –Re2 core complexes, see Re2 core complexes 9+ – transition metal-catalyzed dehydrocoupling 494 –Re3 core complexes 221–220 – σ-andπ-conjugated polymers 493 –(TBA)2Re2Cl8 synthesis 202 – Wurtz coupling, dichlorosilanes 493 rhodium porbitals – catalytic activities 289 –description 17 – chiral dirhodium catalysts 290 – ‘double-bond rule’ 17 – cyclopropanation and cyclopropenation 286, 287 – trans bending, distannenes and distannynes 18, 19 – cyclopropanation reactions 287 porphyrin 245–248, 254 – cyclopropenation 289 – dirhodium metallopeptide catalysts 292 q – functionalization of C–H bonds, see quintuple bonds functionalization of C–H bonds – arylchromium dimers 163 – immobilized dirhodium 292 – dichromium compounds 164, 165 –Ph3C groups 289 – dimolybdenum compounds 165, 166 – Rh–Rh bond 288 – discovery 162, 163 – Rh–Rh single bond 285 – reactivity 170, 171 – synthesis and characterization 285 – structure 166–168 – X-ray crystallography 285 – theoretical studies 169 RPn fragments – as four-electron donor 545–547 r – as two-electron donor 543–545 radial distribution functions, valence orbitals 2 R2Pn fragments 534 reactivity, f-element–metal bonds – group 4 and 5 complexes 535 – deprotonation, see acidic substrates deprotonation – group 5 complexes 536 –description 60 – group 6 and 7 complexes 537, 538 Index 567

– group 9 complexes 541, 542 –UIV–metal bonds stabilization 64 – group 10 and 11 complexes 542, 543 synthetic strategies – organoantimony-/organobismuth–Group 8 metal – bimolecular amine/alkane elimination 79 bond 539, 540 – dimetallic elimination reactions 77 Ru–M heterometallics – early-late heterodinuclear complexes 77 – Ru–group 4 heterometallics 266–268 – salt metathesis 78 – Ru–group 6 heterometallics 267, 268 – Ti–Rh heterodinuclear complex 79 – Ru–group 9 heterometallics 269 –Ti/Zr/Hf–Ircomplexes 78 – Ru–(groups 10, 11) heterometallics 270, 271 Ru–Ru bond distances 240 t 4+ Tc 2 core complexes s – CASSCF/CASPT2 calculations 198 salt elimination 465, 466 – description 196 – f-element–MM bond formation, see f-element–MM – experimental band maxima (cm−1), assignments, bond formation calculated excitation energies 199 – f-element–TM bond formation, see f-element–TM – structure 197 5+ bond formation Tc 2 core complexes 3− s-block, group 13 metal bonds – active orbitals for Tc2X8 (X = Cl, Br) 195 – group 1 metal complexes, see group 1 metal – CASPT2/VTZP level of theory 195 complexes – description 193 3− – group 2 metal complexes 457, 458 –Tc2Br8 anion 194 3− 3− s-block metal–group 14 metal bonds –Tc2Cl8 in HCl(aq) and Tc2Br8 in HBr(aq) 196 6+ – description 499 Tc 2 core complexes – E–M bonded compounds, type [(R3E)nMLm] 500 – acetate derivative Tc2(O2CCH3)4Cl2 189 C− 2− – ion-separated/-paired Ph3 anions 500 – active orbitals, Tc2Br8 187, 188 – structurally characterized complexes with bonding – average Tc–Tc, Tc–X and Tc–L bond distances 187 arrangements 501 – description 186 Sb–Sb and Bi–Bi bonds complexes – emission spectra 189, 190 – distibines and dibismuthines, see distibines and – experimental band maxima (cm−1)andproposed dibismuthines assignments 188, 189 2− – cyclo-organobismuthines 523, 524 –Tc2Br8 anion 187 – M–Sb and M–Bi bonds, see M–Sb and M–Bi bonds –Tc2(O2CCH3)2Cl4 – Pn–Pn (Pn=Sb, Bi) multiple bonds, see Pn–Pn – – active orbitals 192 (Pn=Sb, Bi) multiple bonds ––CH2Cl2 193 – reactivity 526–529 ––structure 191 – thermal and photochemical stability 525, 526 –Tc2(O2CCH3)4Cl2 190 2− 2− silver(I)–silver(I) interactions –Tc2Cl8 and Tc2Br8 in CH2Cl2 188, 189 – Ag–Ag distances 404 – VTZP basis set 187 – Ag–C–Ag moiety 404 technetium – dinuclear complex 404 – β-TcCl2 and α-TcCl2 chains 201 6+ 6+ – metal–ligand bonding 403 –complexeswithaTc2 core, see Tc 2 core – NHC ligands 404 complexes – NMR spectroscopy 404 – ﬁrst man-made element 185 – silver-based coordination polymers 406 –Na[Tc6Br12]2Br 201, 202 single and partial–single bonds (Tm-E) 505, 508 – structure, α-TcCl3 200 4+ 4+ single bonds (E–E) –Tc2 core complexes, see Tc 2 core complexes 5+ 5+ – molecules and oligomers 491 –withTc2 core complexes, see Tc 2 core complexes –polymers,see polymers – 99Tc isotope 186 solid state structures time-resolved infrared studies (TRIR) – bulky amides [RE{N(SiMe3)2}3]63 – amidinate ligands 157 –factors 64 – charge distribution 158 – f-element–main group metal bond lengths 64–66 – electronic absorption and triplet emission spectra – f-element–transition metal bond lengths 64, 67, 68 160 – heterometallic compounds 63 – experimental and calculated values 156, 161 – Ln–MM/TM complexes 64 – frontier molecular orbital energy level 159 –Sm–Gacomplex 64 – homoleptic compounds 158 –stericstrains 64 – infrared spectrum 156 568 Index

time-resolved infrared studies (TRIR) (contd.) v – MLCT 156 vanadium complexes –O2CR ligands 156 – borohydride reduction 91 – photoexcited states 157, 158 – carbonyl compounds 92 – recorded in THF 161 – chalcogenide clusters 97–99 – tungsten 157 – hydride,alkyl and aryl complexes 95–97 transient group 2 metal(I)–metal(I) bonded dimers – ClMgMgCl and ⋅MgCl radicals 29 y – diamagnetic magnesium(I) dimers RMgMgX 29 ytterbium–tin bonds, salt elimination 51 – PhMMPh 28 transition metal–group 14 bonds z – double bonds (Tm=E) 508, 509 Zintl compounds 4− – single and partial–single bonds (Tm-E) 505, 508 – closo-[(E9)M(CO)3] 486, 488 –triplebonds(Tm≡E) 510, 511 – d-block organometallic fragments 486, 487 4− trigonal complexes 249 –[E]4 anions 1 486 triple–bonded species – electron-deﬁcient, ligand-supported clusters – description 533 490 x− – 40 structure and bonding description 533 – homatomic [E]n anions 485 triple bonds (E≡E) 497 – ligand-free E-atoms, ligand elimination 489 – germyne 59 reactions Reactions 498, 499 – ligand-stabilized electron-precise cages 489 4− – Robinson’s bonding model 498 –[Sn]9 with [Ir(cod)Cl]2 488, 489 – trans-bent arrangements group 14 REER 498 – structurally-characterized group 14 485, 486 triple bonds (Tm≡E) 510, 511 –structures[E]9-based anions 486, 487 Zr–Co heterodinuclear complexes 80 u ultrashort Cr–Cr quintuple bonds 9 unsupported gold(I)–gold(I) interactions 412