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The Organometallic Chemistry of the Transition Metals
Robert H. Crabtree (Author)
9781119878513, Wiley
Hardback, published 5 March 2026
576 pages
25.9 x 18.5 x 3.6 cm, 0.953 kg
Continuing a bestselling text’s legacy of presenting our current understanding of d block organometallic compounds, their reactivity, and use in synthesis Fully updated to reflect recent advances, the 8th edition of The Organometallic Chemistry of the Transition Metals provides readers with a comprehensive introduction to the principles and general properties of organometallic compounds as well as practical information on reaction mechanisms and detailed descriptions of contemporary applications. Maintaining the style from prior editions, the author replaces older or dated citations with current ones and changes coverage of the subject to keep the material up to date. The new edition emphasizes such growing topics as organic applications, nanoclusters, electro- and photo-catalysis, computational studies, radical pathways, spin state effects, molecular electronics, proton coupled electron transfer, and alternative energy applications. It also adds new X-ray techniques and computational aspects that can help students design more detailed experiments. Sample topics covered in The Organometallic Chemistry of the Transition Metals include: A long-time bestseller, this new edition of The Organometallic Chemistry of the Transition Metals continues to be the leading textbook on the subject for advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry and practicing chemists in related fields.
Preface xi List of Abbreviations xiii Periodic Table of the Elements xvii 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 σ-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 (NHC) 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 Perfluorocarbon Ligands 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 12-Additions and Eliminations 214 References 215 Problems 216 7 Insertion and Elimination 219 7.1 Introduction 219 7.2 11-Insertion 221 7.3 12-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 1Hand 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 438 14.5 Hydrogenation 440 14.6 Oxidation 442 14.7 Carbonylation 444 14.8 Photoredox Catalysis 445 14.9 Alkyne and Aryne Chemistry 448 14.10 Radical Chemistry 450 14.11 Hydroboration 450 14.12 Electrosynthesis 451 14.13 Isotope Exchange 452 References 453 Problems 457 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
Subject Areas: Chemistry [PN]
