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Preface xi Acknowledgments xiii List of Abbreviations xv 1 Introduction 1 1.1 Why Study Organometallic Chemistry? 1 1.2 Coordination Chemistry 3 1.3 Werner Complexes 3 1.4 The Trans Effect 7 1.5 Soft Versus Hard Ligands 9 1.6 The Crystal Field 10 1.7 The Ligand Field 17 1.8 Two-Electron Three-Center Bonding 19 1.9 Four-Electron Three-Center Bonding 20 1.10 Back Bonding 22 1.11 Trends in d Orbital Energies 26 1.12 Types of Ligand 27 References 32 Problems 33 2 Making Sense of Organometallics 35 2.1 The 18-Electron Rule 35 2.2 Limitations of the 18-Electron Rule 43 2.3 Electron Counting in Reactions 45 2.4 The Oxidation State Concept and its Limitations 46 2.5 Electroneutrality 52 2.6 Coordination Number and Geometry 53 2.7 Effects of Complexation 56 2.8 Differences between Metals 58 References 62 Problems 63 3 Alkyls and Hydrides 65 3.1 Alkyls and Aryls 65 3.2 Other -Bonded Ligands 79 3.3 Metal Hydrides 80 3.4 Sigma Complexes 83 3.5 Bond Strengths 86 References 88 Problems 89 4 Ligand Substitution 91 4.1 Metal Carbonyls 91 4.2 Phosphines 100 4.3 N-Heterocyclic Carbenes 103 4.4 Dissociative Substitution 105 4.5 Associative Substitution 109 4.6 Redox Effects and Interchange Substitution 111 4.7 Photochemical Substitution 113 4.8 Counterions and Solvents in Substitution 115 References 116 Problems 118 5 Pi Complexes 121 5.1 Alkene and Alkyne Complexes 121 5.2 Allyl Complexes 126 5.3 Diene Complexes 130 5.4 Cyclopentadienyl Complexes 133 5.5 Arenes and Other Alicyclic Ligands 140 5.6 Metalacycles 143 5.7 Stability of Polyene and Polyenyl Complexes 144 References 145 Problems 145 6 Oxidative Addition and Reductive Elimination 147 6.1 Introduction 147 6.2 Concerted Additions 149 6.3 SN2 Pathways 152 6.4 Radical Mechanisms 153 6.5 Ionic Mechanisms 155 6.6 Reductive Elimination 156 6.7 Sigma Bond Metathesis 162 6.8 Ligand-Assisted 1,2-Additions and Eliminations 163 6.9 Oxidative Coupling 164 6.10 Proton-Coupled Electron Transfer 165 References 166 Problems 167 7 Insertion and Elimination 169 7.1 Introduction 169 7.2 1,1-Insertion 171 7.3 1,2-Insertion 175 7.4 Outer Sphere Insertions 179 7.5 -, -, - and -Elimination 180 References 182 Problems 182 8 Addition and Abstraction 185 8.1 Introduction 185 8.2 Nucleophilic Addition to CO 187 8.3 Nucleophilic Addition to Polyenes and Polyenyls 189 8.4 Nucleophilic Abstraction 196 8.5 Electrophilic Addition and Abstraction 197 8.6 Single-Electron Transfer and Radical Reactions 200 References 201 Problems 202 9 Homogeneous Catalysis 205 9.1 Catalytic Cycles 205 9.2 Alkene Isomerization 211 9.3 Hydrogenation 213 9.4 Alkene Hydroformylation 221 9.5 Alkene Hydrocyanation 223 9.6 Alkene Hydrosilylation 224 9.7 Coupling Reactions 225 9.8 Organometallic Oxidation Catalysis 227 9.9 Electrocatalysis 229 9.10 Photoredox Catalysis 229 9.11 Surface Supported Single-Atom and Cooperative Catalysis 231 References 233 Problems 235 10 Physical Methods 239 10.1 Mechanism 239 10.2 1H NMR Spectroscopy 240 10.3 13C NMR Spectroscopy 243 10.4 31P NMR Spectroscopy 244 10.5 Dynamic NMR 246 10.6 Spin Saturation Transfer 249 10.7 T1 and the Nuclear Overhauser Effect 250 10.8 IR Spectroscopy 254 10.9 Crystallography 256 10.10 Electrochemistry and EPR 257 10.11 Computation 259 10.12 Other Methods 260 References 262 Problems 263 11 M-L Multiple Bonds 265 11.1 Carbenes 265 11.2 Schrock Carbenes 272 11.3 Carbynes 276 11.4 Bridging Carbenes and Carbynes 278 11.5 N-Heterocyclic Carbenes 279 11.6 Multiple Bonds to Heteroatoms 282 References 285 Problems 286 12 Metathesis Polymerization and Bond Activation 289 12.1 Alkene Metathesis 289 12.2 Alkene Dimerization, Oligomerization, and Polymerization 295 12.3 Activation of CO and CO2 301 12.4 C H Activation 305 12.5 Dehydrogenative Oxidation and Hydrogen Borrowing 309 References 311 Problems 313 13 Green Energy and Materials Applications 317 13.1 Green Chemistry 317 13.2 Energy Chemistry 320 13.3 Clusters and Nanoparticles 323 13.4 Organometallic Materials 325 References 332 Problems 334 14 Organic Applications 337 14.1 Carbon-Carbon and Carbon-Heteroatom Coupling 338 14.2 Metathesis 343 14.3 Cyclopropanation and C-H Insertion 345 14.4 Hydrogenation 346 14.5 Carbonylation 348 14.6 Oxidation 350 14.7 C-H Activation 352 14.8 Click Chemistry and Cycloaddition 355 14.9 Photoredox Catalysis 356 References 359 Problems 360 15 Paramagnetic and High-Oxidation-State Complexes 363 15.1 Magnetism and Spin States 364 15.2 Cyclopentadienyl Complexes 371 15.3 f-Block Complexes 373 References 380 Problems 381 16 Bioorganometallic Chemistry 383 16.1 Introduction 384 16.2 Coenzyme B12 388 16.3 Nitrogen Fixation 394 16.4 Nickel Enzymes 402 16.5 Artificial Enzymes 407 16.6 Biomedical and Biocatalytic Applications 407 References 410 Problems 412 Appendix A: Useful Texts on Allied Topics 415 Appendix B: Major Reaction Types 419 Solutions to Problems 421 Index 437

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