Preface xi List of Abbreviations xiii 1 Introduction 1 1.1 Why Study Organometallic Chemistry?, 2 1.2 Coordination Chemistry, 3 1.3 Werner Complexes, 5 1.4 The Trans Effect, 9 1.5 Soft Versus Hard Ligands and Metals, 11 1.6 The Crystal Field, 13 1.7 The Ligand Field, 24 1.
8 Two-Electron, Three-Center Bonding, 26 1.9 Back Bonding, 26 1.10 Choice of Metals, 30 1.11 The sd n Model and Hypervalent Bonding, 32 References, 37 Problems, 39 2 Making Sense of Organometallics 41 2.1 Valence Electron Counting, 41 2.2 The 18-Electron "Rule", 44 2.3 Electron Counting for Common Ligands, 45 2.4 Bridging Ligands, 49 2.
5 Zero-Electron Ligands, 51 2.6 Limitations of the 18-Electron Rule, 54 2.7 Electron Counting in Reactions, 57 2.8 The Oxidation State Concept and its Limitations, 59 2.9 Coordination Number and Geometry, 65 2.10 Effects of Complexation on Ligands, 67 2.11 Differences between Metals, 71 2.12 Ligand Types, 76 2.
13 Noninnocent Ligands and Ambiguous Oxidation States, 83 References, 85 Problems, 87 3 Alkyls, Aryls, and Hydrides 89 3.1 Stability of Alkyls and Aryls, 89 3.2 Making Alkyls and Aryls, 98 3.3 Other Ï-Bonded Ligands, 106 3.4 Metal Hydrides, 108 3.5 Sigma Complexes, 111 3.6 Metal-Ligand Bond Strengths, 115 References, 118 Problems, 121 4 Ligands and Substitution 123 4.1 Metal Carbonyls: Structure and Bonding, 123 4.
2 Metal Carbonyls: Synthesis and Reactivity, 127 4.3 Bridging Carbonyls and Co Analogues, 130 4.4 NITROSYLS, 132 4.5 Phosphines and Related P-Donor Ligands, 135 4.6 N -Heterocyclic Carbenes (NHCs), 139 4.7 Dissociative Substitution, 140 4.8 Associative Substitution, 145 4.9 Redox Effects and Interchange Substitution, 147 4.
10 Photochemical Substitution, 149 4.11 Other Factors in Substitution, 152 4.12 Metal-Ligand Cooperativity, 154 References, 155 Problems, 157 5 PI-Complexes 159 5.1 Alkene and Alkyne Complexes, 159 5.2 Allyl Complexes, 166 5.3 Diene Complexes, 170 5.4 Cyclopentadienyl Complexes, 172 5.5 Arenes and Related Ligands, 180 5.
6 Metallacycles, 183 5.7 Polyene versus Polyenyl Complexes, 184 5.8 The Isolobal Analogy, 184 References, 185 Problems, 186 6 Oxidative Addition and Reductive Elimination 189 6.1 General Principles, 189 6.2 Concerted Additions, 192 6.3 SN2 Pathways, 195 6.4 Radical Mechanisms, 197 6.5 Ionic Mechanisms, 200 6.
6 Reductive Elimination, 202 6.7 Some Catalytic Applications of OA/RE Sequences, 208 6.8 Sigma Bond Metathesis, 212 6.9 Oxidative Coupling, 213 6.10 Ligand-Assisted 1,2-Additions and Eliminations, 214 References, 215 Problems, 216 7 Insertion and Elimination 219 7.1 Introduction, 219 7.2 1,1-Insertion, 221 7.3 1,2-Insertion, 226 7.
4 Outer Sphere Insertions, 229 7.5 Beta Elimination and Related Processes, 231 7.6 Alkene Isomerization Catalysis, 233 7.7 Dehydrogenative Oxidation and Hydrogen Borrowing Catalysis, 236 References, 239 Problems, 240 8 Addition and Abstraction 243 8.1 Types of Reaction, 243 8.2 Nucleophilic Addition to CO, 246 8.3 Nucleophilic Addition to Polyenes and Polyenyls, 248 8.4 The Wacker Process, 252 8.
5 Nucleophilic Abstraction and Deprotonation, 254 8.6 Electrophilic Addition and Abstraction, 256 8.7 Electron Transfer and Radical Pathways, 259 8.8 Proton-coupled Electron Transfer, 260 References, 263 Problems, 264 9 Homogeneous Catalysis 267 9.1 Catalytic Cycles, 268 9.2 Catalytic Hydrogenation, 275 9.3 Alkene Hydroformylation, 284 9.4 Alkene Hydrocyanation, 286 9.
5 Alkene Hydrosilylation, 287 9.6 Cross-Coupling Reactions, 288 9.7 Oxidation Catalysis, 292 9.8 Electrocatalysis, 294 9.9 Photoredox Catalysis, 295 9.10 Catalyst Decomposition and Deactivation, 298 References, 299 Problems, 303 10 Physical Methods 307 10.1 Mechanism, 307 10.2 1H and 2H NMR Spectroscopy, 309 10.
3 13C NMR Spectroscopy, 315 10.4 31P NMR Spectroscopy, 315 10.5 Dynamic NMR, 318 10.6 Electron Paramagnetic Resonance Spectroscopy, 320 10.7 IR Spectroscopy, 323 10.8 Structure Determination, 327 10.9 Electrochemistry, 329 10.10 Computation, 330 10.
11 Big Data, Artificial Intelligence, and Machine Learning, 331 10.12 Other Methods, 332 References, 334 Problems, 337 11 Carbenes, Carbynes, and M-L Multiple Bonding 339 11.1 Carbenes, 339 11.2 Carbynes, 350 11.3 Bridging Carbenes and Carbynes, 352 11.4 N -Heterocyclic Carbenes, 353 11.5 Carbide and Carbone Complexes, 357 11.6 Multiple Bonds to Heteroatoms, 358 References, 361 Problems, 362 12 Metathesis, Polymerization, and Bond Activation 365 12.
1 Alkene Metathesis, 365 12.2 Alkene Dimerization, Oligomerization, and Polymerization, 372 12.3 Activation of CO and CO2, 380 12.4 C-H Activation and Functionalization, 384 References, 390 Problems, 391 13 Green, Energy & Materials Applications 395 13.1 Green Chemistry, 395 13.2 Organometallics for an Alternative Energy Future, 401 13.3 Metal-Metal Bonds and Clusters, 404 13.4 Nanoparticles, 407 13.
5 Organometallic Materials, 409 13.6 Supported Organometallics, 415 References, 417 Problems, 420 14 Organic Applications 423 14.1 Carbon-Carbon and Carbon-heteroatom Coupling, 424 14.2 C-H Activation and Late-stage Functionalization, 431 14.3 Metathesis of C==C Bonds, 436 14.4 Carbenes in Cyclopropanation and C-H Insertion, 439 14.5 Hydrogenation, 441 14.6 Oxidation, 443 14.
7 Carbonylation, 445 14.8 Photoredox Catalysis, 446 14.9 Alkyne and Aryne Chemistry, 449 14.10 Radical Chemistry, 451 14.11 Hydroboration, 451 14.12 Electrosynthesis, 452 14.13 Isotope Exchange, 453 References, 454 Problems, 458 15 High Oxidation States, Magnetism, and the f-Block 461 15.1 High Oxidation States, 461 15.
2 Magnetism and Spin States, 463 15.3 Cyclopentadienyl Complexes, 472 15.4 The f-block, 475 References, 484 Problems, 485 16 Bioorganometallic Chemistry 487 16.1 Introduction, 488 16.2 Coenzyme B12, 495 16.3 Iron-sulfur Clusters, 501 16.4 Nitrogen Fixation, 504 16.5 Nickel Enzymes, 511 16.
6 Applications to Chemical Biology, 516 16.7 Biomedical and Biocatalytic Applications, 517 References, 521 Problems, 524 Appendix A: Useful Texts on Allied Topics 527 Appendix B: Major Reaction Types 529 Answers 531 Index 549.