Organometallic chemistry : fundamentals and applications of organometallic compounds

This book provides the reader with a comprehensive introduction to the topic of organometallic chemistry. With an easy to follow structure covering both nontransition metals and transition metals as well as the applications of organometallic reagents in organic synthesis, this book is a must-have for the organometallic chemist. * Thematic overview of organometallic compounds of transition and non-transition metals. * Covers structures as well as applications. Cover Half Title Also of Interest Organometallic Chemistry: Fundamentals and Applications of Organometallic Compounds Copyright Foreword Contents Part I: General 1. The scope of organometallic chemistry 2. Organometallic molecules: the nature of metal–carbon bonds 2.1 Sigma-covalent (bicentric bielectronic) metal–carbon bonds 2.2 Highly polar and ionic metal–carbon bonds 2.3 Electron-deficient (localized tricentric bielectronic) metal–carbon bonds 2.4 Delocalized bonds in polynuclear systems 2.5 Sigma donor–π-acceptor dative bonds 2.6 π-Bonding of unsaturated molecules to transition metal atoms 2.7 Carbenes, carbynes, carbones, and carbides 2.7.1 Carbenes 2.7.2 Carbynes 2.7.3 Carbones 2.7.4 Carbides Further reading References 3. Supramolecular organometallic association Further reading 4. Inverse organometallic compounds References Part II: Organometallic compounds of main group metals 5. Organometallic compounds of group 1 (alkali metals) 5.1 Organolithium compounds 5.2 Organometallic derivatives of sodium and heavier alkali metals Further reading Reference 6. Organometallic compounds of group 2 metals (rare earths) 6.1 Organoberyllium compounds 6.1.1 Homoleptic compounds BeR2 6.1.2 Hypervalent species [BeR3]– and [BeR4]2– 6.1.3 Diorganoberyllium donor adducts R2Be.D 6.1.4 Organoberyllium halides, RBeX 6.1.5 Functional organoberyllium compounds, RBeX Further reading 6.2 Organomagnesium compounds 6.2.1 Homoleptic compounds, MgR2 6.2.2 Hypervalent anions [MgR3]– 6.2.3 Subvalent cations [RMg]+ 6.2.4 Organomagnesium donor adducts MgR2.D 6.2.5 Inverse organomagnesium compounds 6.2.6 Organomagnesium halides 6.2.7 Functional organomagnesium compounds RMgX Further reading 6.3 Organometallic compounds of calcium 6.3.1 Homoleptic CaR2 compounds 6.3.2 Hypervalent [CaR3]– anions 6.3.3 Other organocalcium compounds 6.4 Organostrontium and -barium compounds Further reading References 7. Organometallic compounds of group 13 metals 7.1 Organoaluminum compounds 7.1.1 Homoleptic compounds, AlR3 7.1.2 Hypervalent species (anions), [AlR4]– 7.1.3 Subvalent cations, [MR2]+ 7.1.4 Triorganoaluminum donor adducts, AlR3.D 7.1.5 Inverse organoaluminum compounds 7.1.6 Organoaluminum inverse coordination complexes 7.1.7 Organoaluminum R2AlH hydrides 7.1.8 Organoaluminum R2AlX halides 7.1.9 Organoaluminum functional derivatives (alkoxides, thiolates and amides) 7.1.10 Compounds with Al–Al bonds 7.2 Organogallium compounds 7.2.1 Homoleptic derivatives, GaR3 7.2.2 Hypervalent anions 7.2.3 Subvalent cations 7.2.4 Inverse organogallium compounds 7.2.5 Diorganogallium halides, R2GaX 7.2.6 Diorganogallium hydroxides, R2GaOH 7.2.7 Diorganogallium functional derivatives 7.2.8 Organogallium inverse coordination complexes 7.3 Organoindium compounds 7.3.1 Homoleptic compounds, lnR3 7.3.2 Diorganoindium halides, R2lnX 7.3.3 Functional diorganoindium derivatives 7.4 Organothallium compounds 7.4.1 Homoleptic derivatives, TIR3 7.4.2 Monovalent organothallium compounds, TlR 7.4.3 Diorganothallium halides, R2TlX 7.4.4 Functional diorganothallium compounds, R2TlX′ 7.4.5 Functional monoorganothallium compounds, RTlX2 Further reading References 8. Organometallic compounds of group 14 metals 8.1 Organotin compounds 8.1.1 Homoleptic species 8.1.2 Hypervalent penta- and hexa-organotin compounds 8.1.3 Diorganotin species 8.1.4 Tin π-complexes 8.1.5 Inverse organotin compounds 8.1.6 Organotin hydrides, RnSnH4–n 8.1.7 Organotin halides, RnSnX4–n 8.1.8 Organostannoxanes (organotin oxides) 8.1.9 Organotin hydroxides, RnSn(OH)4–n 8.1.10 Organotin alkoxides (RnSn(OR′)4–n) and related compounds 8.1.11 Organotin sulfides, selenides and tellurides 8.1.12 Organotin thiolates, RnSn(SR′)4–n 8.1.13 Organotin amino-derivatives, RnSn(NR′R′′)4–n 8.1.14 Organostannazanes 8.1.15 Organotin inverse coordination complexes 8.1.16 Organodi- and poly-stannanes Further reading 8.2 Organolead compounds 8.2.1 Homoleptic compounds, PbR4 8.2.2 Heterocycles with lead heteroatoms 8.2.3 Subvalent species 8.2.4 Inverse organolead compounds 8.2.5 Organolead halides, RnPbX4–n 8.2.6 Organolead hydroxides, RnPb(OH)4–n 8.2.7 Organolead oxides 8.2.8 Organolead alkoxides 8.2.9 Organolead carboxylates, RnPb(OCOR′)4–n 8.2.10 Organolead sulfide 8.2.11 Organolead thiolates RnPb(SR’)4–n 8.2.12 Organolead compounds with Pb–Pb bonds References 9. Organometallic compounds of group 15 metals 9.1 Organoantimony compounds 9.1.1 Homoleptic compounds, SbR3 9.1.2 Organoantimony heterocycles 9.1.3 Pentavalent SbR5 compounds 9.1.4 Subvalent stibonium [SbvR4]+ cations 9.1.5 Hypervalent SbV anions: hexasubstituted anions, [SbR6]– 9.1.6 Inverse organoantimony compounds 9.1.7 Organoantimony(III) halides 9.1.8 Oxygen-containing organoantimony compounds 9.1.9 Sulfur-containing organoantimony compounds 9.1.10 Nitrogen-containing organoantimony compounds 9.1.11 Organoantimony compounds with Sb–Sb bonds 9.1.12 Organoantimony(III) compounds as donor ligands 9.1.13 Organoantimony inverse coordination complexes Further reading 9.2 Organobismuth compounds 9.2.1 Homoleptic BiR3 compounds 9.2.2 Pentaorgano-substituted derivatives, BiR5 9.2.3 Subvalent bismuth cations, [BiVR4]+ 9.2.4 Organobismuth halides 9.2.5 Oxygen-containing organobismuth compounds References 10. Organometallic compounds of group 12 metals 10.1 Organozinc compounds 10.1.1 Homoleptic compounds, ZnR2 10.1.2 Hypervalent anions [ZnR3]– and [ZnR4]2– 10.1.3 Diorganozinc donor adducts, R2Zn.D 10.1.4 Organozinc hydrides, RZnH 10.1.5 Organozinc halides, RZnX 10.1.6 Organozinc alkoxides 10.1.7 Organozinc amides 10.1.8 Compounds with Zn–Zn bonds 10.1.9 Inverse coordination organozinc complexes 10.2 Organocadmium compounds 10.2.1 Homoleptic compounds, CdR2 10.2.2 Hypervalent anions, [CdR3]– 10.2.3 Diorganocadmium donor adducts, CdR2.D 10.2.4 Organocadmium halides, RCdX 10.2.5 Organocadmium functional compounds, RCdX′ 10.3 Organomercury compounds 10.3.1 Homoleptic compounds, HgR2 10.3.2 Organomercury heterocycles 10.3.3 Diorganomercury donor adducts, HgR2.D 10.3.4 Organomercury halides 10.3.5 Organomercury hydroxides, RHgOH 10.3.6 Organomercury alkoxides, RHg-OR′ 10.3.7 Organomercury sulfides 10.3.8 Inverse organomercury compounds 10.3.9 Organomercury inverse coordination complexes 10.3.10 Compounds with Hg–Hg bonds References Part III: Organometallic compounds of transition metals 11. Organometallic compounds with two electron ligands 11.1 Metal carbonyls 11.1.1 The structure of metal carbonyls 11.1.2 Preparation of metal carbonyls 11.1.3 Metal–carbonyl anions 11.1.4 Metal–carbonyl cations 11.1.5 Metal carbonyl halides 11.2 Metal thiocarbonyls 11.3 Metal selenocarbonyls 11.4 Metal–isocyanide complexes 11.5 Metal–carbene complexes and related compounds 11.6 Olefinic complexes 11.6.1 Monoolefin complexes 11.6.2 Bis(olefin) complexes 11.6.3 Tris(olefin) and tetrakis(olefin) complexes 11.6.4 Bidentate diolefin complexes 11.6.5 Bridging diolefin complexes 11.6.6 Tridentate olefin complexes References 12. Compounds with three-electron ligands 12.1 Allylic complexes and related compounds 12.1.1 Homoleptic allyl metal complexes 12.1.2 Complexes with bridging allylic ligands 12.1.3 Heteroleptic mixed allyl–ligand metal complexes 12.1.4 Allylic fragments in cyclic polyolefins 12.2 Cyclopropenyl complexes References 13. Compounds with four-electron ligands 13.1 Butadiene complexes and related compounds 13.2 Cyclobutadiene complexes 13.3 Complexes with cyclic dienes and polyenes 13.3.1 Cyclohexadiene 13.3.2 Cycloheptadiene-1,3 13.3.3 Cyclooctatriene 13.3.4 Cyclooctatetraene 13.3.5 Complexes with heteroatom molecules as four-electron ligands 13.4 Trimethylenemethyl radical as a four-electron ligand References 14. Compounds with five-electron ligands 14.1 Metallocene complexes 14.1.1 Ferrocene Further reading 14.1.2 Other metallocenes 14.1.3 Cyclopentadienylmetal carbonyls and carbonyl halides References 15. Six-electron ligands 15.1 Homoleptic sandwich complexes Further reading 15.2 Heteroleptic, mixed ligand sandwich compounds 15.3 Sandwich ηn-complexes of some heterocyclic ligands 16. Complexes with seven-electron ligands 17. Complexes with eight-electron ligands Reference 18. Inverse sandwich complexes 18.1 Cyclobutadiene center 18.2 Cyclopentadiene center 18.3 Benzene center 18.4 Cyclooctatetraene center 18.5 Fused arene rings as centers References 19. Organometallic compounds with σ-transition metal–carbon bonds 19.1 General 19.2 Homoleptic compounds 19.2.1 Titanium, zirconium, hafnium 19.2.2 Vanadium, niobium, tantalum 19.2.3 Chromium, molybdenum, tungsten 19.2.4 Manganese, technetium, rhenium 19.2.5 Iron, ruthenium, osmium 19.2.6 Cobalt, rhodium, iridium 19.2.7 Nickel, palladium, platinum 19.2.8 Copper, silver, gold 19.3 Heteroleptic compounds 19.3.1 Organometallic halides 19.3.2 Nitrogen donors 19.3.3 Phosphines 19.3.4 Metal carbonyl derivatives, (CO)mMRn 19.3.5 Cyclopentadienylmetal derivatives, (η5-C5H5)mMRn, and cyclopentadienylmetal carbonyl derivatives, (η5-C5H5)MRn(CO)m 19.3.6 Metallacycles and chelate rings References Part IV: Application of organometallics in organic synthesis 20. Polar organometallics in organic syntheses 20.1 Reactivity of polar organometallics 20.1.1 General 20.1.2 Ortho-metallation 20.1.3 Organomagnesium reagents 20.1.4 Alkali-metal-mediated reactions 20.1.5 Turbo-Grignard reagents and related salt-supported complexes 20.2 Organotitanium reagents in organic synthesis 20.2.1 Reactivity of organotitanium reagents 20.2.2 Titanium-based reagents for carbonyl methylenation and alkylidenation References 21. Transition metal organometallics in organic syntheses 21.1 Specific reaction types involving transition metal organometallics 21.1.1 Oxidative addition–reductive elimination 21.1.2 Migratory insertion and β-hydride elimination 21.1.3 Nucleophilic attack on coordinated substrates 21.2 Carbon–carbon bond formation reactions 21.2.1 Cross-coupling reactions – general 21.2.2 The Kumada–Tamao–Corriu cross-coupling reactions 21.2.3 The Negishi cross-coupling reactions 21.2.4 The Stille cross-coupling reactions 21.2.5 The Suzuki–Miyaura cross-coupling reactions 21.2.6 The Hiyama–Denmark cross-coupling reactions 21.2.7 The Murahashi–Feringa cross-coupling reactions 21.2.8 Sonogashira cross-coupling reactions 21.3 The Mizoroki–Heck reaction 21.4 Hydroformylation 21.4.1 Asymmetric hydroformylation 21.5 Hydrogenation 21.5.1 Asymmetric hydrogenation 21.6 Carbonylation of methanol 21.7 Metathesis reactions 21.7.1 Cross-metathesis (CM) 21.7.2 Ring-closing metathesis (RCM) 21.7.3 Ring-opening metathesis polymerization (ROMP) 21.7.4 Acyclic diene metathesis polymerization (ADMEP) 21.8 Polymerization References Index