Basic Organometallic Chemistry : Concepts, Syntheses, and Applications of Transition Metals Table Of Contents: Foreword v Preface vii List of abbreviations ix Chapter 1 Introduction 1 (15) 1.1 What is organometallic chemistry? 1 (1) 1.2 A brief history of organometallic 2 (5) chemistry 1.3 Importance of organometallic 7 (8) compounds 1.3.1 Organometallic compounds as reagents 7 (3) 1.3.2 Organometallic compounds as 10 (4) additives 1.3.3 Organometallic compounds as 14 (1) catalysts Supplementary reading 15 (1) Chapter 2 The 18 Valence Electron Rule 16 (10) 2.1 Introduction 16 (1)
2.2 The 18 electron rule 16 (1) 2.3 Counting of electrons and finding 17 (4) metal-metal bonds Problems and exercises 21 (4) Supplementary reading 25 (1) Chapter 3 Metal Carbonyls 26 (20) 3.1 Structure, -bonding and infrared 27 (4) spectroscopy 3.2 Bonding modes of CO 31 (1) 3.3 Symmetry of metal carbonyls 32 (1) 3.4 Syntheses of metal carbonyls 32 (3) 3.4.1 Direct carbonylation 33 (1) 3.4.2 Reductive carbonylation 33 (2) 3.5 Reactions of metal carbonyls 35 (5) 3.5.1 Activation of metal carbonyls 35 (1) 3.5.2 Disproportionation 36 (1) 3.5.3 Nucleophilic addition to CO 36 (1) 3.5.4 Electrophilic addition to the 36 (1) carbonyl oxygen 3.5.5 Carbonyl anions, cations and 37 (1) hydrides 3.5.6 Collman's reagent 38 (1) 3.5.7 Migratory insertion of carbonyls 38 (1) 3.5.8 Oxidative decarbonylation 39 (1) 3.5.9 Photochemical substitution 39 (1) 3.5.10 Microwave assisted substitution 40 (1) 3.6 Metal nitrosyls 40 (1) Problems and exercises 41 (3) Supplementary reading 44 (2) Chapter 4 Neutral Spectator Ligands: 46 (14) Phosphines and N-Heterocyclic Carbenes
4.1 Phosphines: steric and electronic 46 (2) parameters 4.2 Basicity of phosphines 48 (2) 4.3 Monodentate phosphines 50 (1) 4.4 Multidentate phosphines 51 (2) 4.5 N-Heterocyclic carbenes 53 (3) Problems and exercises 56 (2) Supplementary reading 58 (2) Chapter 5 Alkenes and Alkynes as Ligands 60 (16) 5.1 Models of ethylene-metal bonding 60 (3) 5.2 Synthesis of metal-alkene complexes 63 (2) 5.3 Reactions of metal bound alkenes: The 65 (1) concept of Umpolung 5.4 Alkynes: modes of bonding to metals 66 (2) 5.5 Reactions of metal complexes of 68 (4) alkenes and alkynes 5.5.1 Pauson-Khand reaction 71 (1) Problems and exercises 72 (2) Supplementary reading 74 (2) Chapter 6 Carbenes and Carbynes: 76 (14) Complexes with Metal-Carbon Double and Triple Bonds 6.1 Metal Carbenes 76 (7) 6.1.1 Synthesis of Fischer carbene 76 (1) complexes 6.1.2 Synthesis of Schrock carbene 77 (3) complexes 6.1.3 Tebbe's reagent 80 (1) 6.1.4 Carbenes that are intermediate 81 (2) between the Fischer and Schrock types 6.2 Metal Carbynes 83 (2)
6.2.1 Synthesis of metal-carbyne 83 (1) complexes 6.2.2 Reactions of metal-carbyne 84 (1) complexes Problems and exercises 85 (4) Supplementary reading 89 (1) Chapter 7 Alkyl, Aryl and Ligands with Higher 90 (27) Hapticity 7.1 σ bonded alkyl groups as ligands 90 (2) 7.1.1 Synthesis of metal-alkyl compounds 90 (1) 7.1.2 β-hydride elimination 91 (1) 7.1.3 σ bonded η1-aryl ligands 92 (1) 7.2 Cyclic and acyclic polyenyl π bonded 92 (19) ligands 7.2.1 Cyclopentadienyl (Cp-) 92 (1) 7.2.2 Synthesis of Cp based sandwich 93 (1) compounds 7.2.3 Structure and properties of MCp2 94 (3) complexes 7.2.4 Ferrocene: The first metal-sandwich 97 (2) compound 7.2.5 Reactions of metal-sandwich 99 (1) compounds 7.2.6 Bent sandwich compounds 100(1) 7.2.7 Schwartz's reagent and 101(1) hydrozirconation 7.2.8 Chemistry of Cp 101(1) 7.2.9 Chemistry of arene sandwich 102(2) compounds 7.2.10 Allyl groups as ligands 104(2) 7.2.11 1,3-Butadiene complexes 106(2)
7.2.12 Cyclobutadiene complexes 108(3) 7.2.13 Cycloheptatriene and 111(1) cyclooctatetraene as ligands 7.3 Davies-Green-Mingos (DGM) rules 111(1) Problems and exercises 112(4) Supplementary reading 116(1) Chapter 8 Unique Reactions in 117(25) Organometallic Chemistry 8.1 Oxidative addition and oxidative 117(4) coupling 8.1.1 Intramolecular oxidative addition: 120(1) C-H activation and cyclometallation 8.1.2 Oxidative coupling 120(1) 8.2 Reductive elimination 121(6) 8.2.1 Mononuclear systems 122(3) 8.2.2 Binuclear systems 125(2) 8.3 Migratory insertion reactions 127(8) 8.3.1 Lewis acid acceleration 128(1) 8.3.2 Redox acceleration 129(1) 8.3.3 Migration versus insertion 129(3) 8.3.4 Insertion of alkenes 132(1) 8.3.5 β-hydrogen elimination versus 133(2) reductive elimination Problems and exercises 135(5) Supplementary reading 140(2) Chapter 9 Ligand Substitution Reactions and 142(24) Fluxionality in Organometallic Compounds 9.1 Types of ligand substitution reactions 142(4) 9.1.1 Activation entropy and activation 143(1) volume 9.1.2 Factors affecting substitution 144(2)
reactions 9.2 Associative substitutions 146(3) 9.2.1 Hapticity change in mulitdentate 147(2) ligands 9.3 Dissociative substitutions 149(1) 9.4 Interchange mechanisms 150(1) 9.4.1 Associative interchange 151(1) 9.4.2 Dissociative interchange 151(1) 9.5 Stereochemical non-rigidity in 151(11) organometallic compounds 9.5.1 Ring whizzing in η1-cp complexes 153(2) 9.5.2 Interchange of η1- and η5-cp rings 155(2) 9.5.3 Allyl complexes 157(1) 9.5.4 Allene complexes 158(1) 9.5.5 Scrambling of carbonyl groups in 159(3) metal carbonyls Problems and exercises 162(2) Supplementary reading 164(2) Chapter 10 Metal Clusters 166(30) 10.1 Introduction 166(1) 10.2 Dinuclear clusters 167(3) 10.2.1 A five fold bonded organometallic 169(1) compound 10.3 Multinuclear carbonyl clusters 170(10) 10.3.1 Low nuclearity carbonyl clusters 170(1) 10.3.2 High nuclearity carbonyl clusters 171(1) (HNCC) 10.3.3 Electron counting schemes for 172(2) high nuclearity clusters 10.3.4 Capping rules 174(1) 10.3.5 Limitations and exceptions 175(1)
10.3.6 Polyhedral skeletal electron pair 176(3) approach or Mingo's rules 10.3.7 Carbide clusters 179(1) 10.4 The isolobal analogy 180(7) 10.4.1 Clusters having interstitial main 186(1) group elements 10.5 Synthesis of metal carbonyl clusters 187(2) 10.6 Reactions of metal carbonyl clusters 189(3) Problems and exercises 192(2) Supplementary reading 194(2) Chapter 11 Homogeneous Catalysis Using 196(15) Organometallic Compounds 11.1 Catalysis 196(2) 11.2 Terminology in catalysis 198(6) 11.2.1 Turnover 198(1) 11.2.2 Turnover number (TON) 199(1) 11.2.3 Turnover frequency (TOF) or 199(5) turnover rate 11.3 Sequences involved in a catalysed 204(1) reaction 11.4 Other important terminology used in 205(1) catalysis 11.5 Asymmetric synthesis using a catalyst 205(1) 11.6 Heterogeneous catalysis 206(2) 11.6.1 Catalytic converters in 207(1) automobiles 11.7 Feedstock for the chemical industry 208(1) Problems and exercises 209(1) Supplementary reading 210(1) Chapter 12 Catalytic Hydrogenation of 211(24) Alkenes and Related Reactions
12.1 Hydrogenation catalysts 211(7) 12.1.1 Classification of hydrogenation 211(2) catalysts 12.1.2 Catalytic cycle of Wilkinson's 213(1) catalyst 12.1.3 Catalytic cycles of iridium and 214(3) ruthenium based catalysts 12.1.4 Directing effects in catalytic 217(1) hydrogenation 12.1.5 Hydrogenation by lanthanide 217(1) organometallic compounds 12.2 Catalytic asymmetric synthesis 218(8) 12.2.1 The first industrial catalytic 219(1) asymmetric hydrogenation 12.2.2 The mechanism of asymmetric 220(1) hydrogenation using a chiral catalyst 12.2.3 Asymmetric hydrogenation of 221(3) ketones and isomerisation 12.2.4 Asymmetric hydrogen transfer 224(2) 12.3 Hydrocyanation of alkenes 226(2) 12.4 Hydrosilylation of alkenes 228(3) Problems and exercises 231(2) Supplementary reading 233(2) Chapter 13 Hydroformylation 235(14) 13.1 Importance of hydroformylation 235(1) 13.2 Cobalt catalysts for hydroformylation 236(2) 13.3 Phosphine modified cobalt catalysts 238(1) 13.4 Rhodium-phosphine catalysts 239(2) 13.5 Factors affecting the n/iso ratio of 241(2) hydroformylation products 13.6 Enantioselective hydroformylation 243(1)
13.7 Carboalkoxylation of olefins 244(2) Problems and exercises 246(2) Supplementary reading 248(1) Chapter 14 Methanol Carbonylation and 249(10) Olefin Oxidation: Monsanto, Cativa and Wacker Processes 14.1 History of methanol carbonylation 249(1) 14.2 The Monsanto process 250(1) 14.2.1 Problems with the Monsato 251(1) process 14.3 Celanese process using Lil modified 251(1) rhodium catalyst 14.4 Tennessee Eastman acetic anhydride 252(1) process 14.5 British Petroleum's Cativa process 252(2) 14.6 The Wacker process 254(3) Problems and exercises 257(1) Supplementary reading 258(1) Chapter 15 Olefin Metathesis 259(27) 15.1 Olefin metathesis as a synthetic tool 259(1) 15.2 Well known olefin metathesis 260(1) catalysts and their properties 15.3 Synthesis of Grubbs' and Schrock 260(6) catalysts 15.4 Mechanism of olefin metathesis 266(9) 15.4.1 Ring opening metathesis (ROM) 267(1) 15.4.2 Cross metathesis (CM) 267(2) 15.4.3 Ring closing metathesis (RCM) 269(2) 15.4.4 Ring opening metathesis 271(1) polymerisation (ROMP) 15.4.5 Acyclic diene metathesis 272(2)
polymerisation (ADMET) 15.4.6 Enyne metathesis (EM) 274(1) 15.5 Comparison of catalysts 275(3) 15.6 Metathesis of hindered olefins 278(1) 15.7 Applications of catalytic olefin 279(2) metathesis Problems and exercises 281(3) Supplementary reading 284(2) Chapter 16 Palladium Catalysed C-C and C-N 286(29) Cross Coupling Reactions 16.1 Discovery of palladium based cross 286(1) coupling reactions 16.2 Industrial applications of cross 287(1) coupling reactions 16.3 The cross coupling catalyst 288(1) 16.4 The Heck reaction 288(3) 16.5 Suzuki-Miyaura coupling 291(4) 16.6 Sonogashira coupling 295(2) 16.7 Stille coupling 297(1) 16.8 Kumada coupling 298(2) 16.9 Negishi coupling 300(2) 16.10 Hiyama coupling 302(1) 16.11 Buchwald-Hartwig C-N cross coupling 303(2) 16.12 Cross coupling reactions in aqueous 305(4) media with functional group tolerance Problems and exercises 309(3) Supplementary reading 312(3) Chapter 17 Olefin Polymerisation and 315(29) Oligomerisation Reactions 17.1 Catalysts for olefin polymerisation 316(1) 17.2 Types of polyethylene and 316(3)
polypropylene 17.2.1 Polyethylene 316(1) 17.2.2 Polypropylene 316(3) 17.3 The Ziegler-Natta catalyst 319(1) 17.4 Site control and chain end control 320(2) mechanisms 17.5 Metallocene based catalysts 322(7) 17.5.1 Polypropylenes using 322(1) metallocenes 17.5.2 The mechanism of propylene 323(2) polymerisation by metallocenes 17.5.3 Polypropylene and 325(1) stereochemistry 17.5.4 Stereo-block polypropylene 326(2) 17.5.5 Constrained geometry catalysts 328(1) 17.6 Post-metallocene catalysts 329(6) 17.6.1 The Brookhart catalysts 329(3) 17.6.2 Fenokishi Imin (FI) and related 332(3) ligand based metal catalysts 17.7 Olefin oligomerisation reactions 335(3) 17.7.1 Shell's higher olefin process 335(3) Problems and exercises 338(4) Supplementary reading 342(2) Chapter 18 Ferrocene: Structure, Bonding 344(25) and Reactions 18.1 Structure and bonding of ferrocene 344(1) 18.2 The reactions of ferrocene and its 345(10) derivatives 18.2.1 Basic chemical reactions of 347(1) ferrocene 18.2.2 Reactions of acetyl ferrocene and 348(2)
formyl ferrocene 18.2.3 Lithiated ferrocenes and their 350(3) reactions 18.2.4 (Dimethylaminomethyl)ferrocene 353(1) and its methiodide salt 18.2.5 Ferrocene boronic acid and 354(1) haloferrocenes 18.3 Ferrocene derivatives in asymmetric 355(8) catalysis 18.3.1 Chirality in ferrocene derivatives 355(3) 18.3.2 Synthesis of chiral ferrocene based 358(5) compounds Problems and exercises 363(2) Supplementary reading 365(4) Chapter 19 Organometallic Polymers 369(32) 19.1 Polymers with organometallic 369(2) moieties as pendant groups 19.2 Polymers with organometallic 371(16) moieties in the main chain 19.2.1 Ferrocene based condensation 371(1) polymers 19.2.2 Condensation polymers based on 372(7) rigid rod polyynes 19.2.3 Polymers prepared by ring 379(8) opening polymerisation process 19.3 Organometallic dendrimers 387(8) 19.3.1 Synthesis of dendrimers: 388(7) Divergent and convergent methods Problems and exercises 395(4) Supplementary reading 399(2) Chapter 20 Bioorganometallic Chemistry 401(30)
20.1 Introduction 401(1) 20.2 Organometallic enzymes and 402(9) coenzymes 20.2.1 Vitamin B12 coenzyme: `Nature's 402(1) most beautiful cofactor' 20.2.2 Nomenclature and structure 403(1) 20.2.3 Correnoid dependant enzymatic 403(6) reactions 20.2.4 Vitamin B12 model compounds 409(2) 20.3 Role of organometallics in heavy metal 411(7) poisoning 20.3.1 Heavy metal toxicity: Mercury 411(3) related cases 20.3.2 Arsenic poisoning 414(4) 20.4 Organometallic compounds as drugs 418(5) 20.4.1 η6-aryl-ruthenium compounds as 418(1) general anticancer drugs 20.4.2 Ferroquine as antimalarial drug 419(2) 20.4.3 Ferrocifen as breast cancer drug 421(2) 20.5 Organometallics as 423(4) radiopharmaceuticals, tracers, ionophores and sensors 20.5.1 Radiopharmaceuticals 423(1) 20.5.2 Organometallic tracers 424(1) 20.5.3 Organometallics as ionophores 424(2) 20.5.4 Organometallic compounds as 426(1) sensors Problems and exercises 427(2) Supplementary reading 429(2) Appendix 1 Solutions to problems and exercises 431(74) Appendix 2 Quick revision questions 505(11)
Appendix 3 Atomic weights of the elements 516(4) Index 520