The Organometallic Chemistry of the Transition Metals

Robert H. Crabtree, PhD, is a professor in the Department of Chemistry at Yale University.

Acknowledgment x List of Abbreviations xi 1 Introduction 1 1.1 Why Study Organometallic Chemistry?, 1 1.2 Coordination Chemistry, 2 1.3 Werner Complexes, 3 1.4 The Trans Effect, 7 1.5 Soft versus Hard Ligands, 8 1.6 The Crystal Field, 9 1.7 The Ligand Field, 16 1.8 Back Bonding, 19 1.9 Electroneutrality, 23 1.10 Types of Ligand, 25 2 General Properties of Organometallic Complexes 33 2.1 The 18-Electron Rule, 33 2.2 Limitations of the 18-Electron Rule, 39 2.3 Electron Counting in Reactions, 41 2.4 Oxidation State, 42 2.5 Coordination Number and Geometry, 46 2.6 Effects of Complexation, 49 2.7 Differences between Metals, 52 2.8 Supramolecular Chemistry, 54 3 Metal Alkyls, Aryls, and Hydrides and Related s -Bonded Ligands 58 3.1 Transition Metal Alkyls and Aryls, 58 3.2 Related s-Bonded Ligands, 73 3.3 Metal Hydride Complexes, 75 3.4 sigma Complexes, 78 3.5 Bond Strengths for Classical sigma-Bonding Ligands, 82 4 Carbonyls, Phosphine Complexes, and Ligand Substitution Reactions 88 4.1 Metal Complexes of CO, RNC, CS, and NO, 88 4.2 Phosphines and Related Ligands, 99 4.3 Dissociative Substitution, 104 4.4 Associative Substitution, 108 4.5 Redox Effects, The I Mechanism, and Rearrangements in Substitution, 111 4.6 Photochemical Substitution, 114 4.7 Steric and Solvent Effects in Substitution, 117 5 Complexes of p -Bound Ligands 122 5.1 Alkene and Alkyne Complexes, 122 5.2 Allyl Complexes, 128 5.3 Diene Complexes, 132 5.4 Cyclopentadienyl Complexes, 136 5.5 Arenes and Other Alicyclic Ligands, 143 5.6 Metalacycles and Isolobal Replacement, 148 5.7 Stability of Polyene and Polyenyl Complexes, 149 6 Oxidative Addition and Reductive Elimination 153 6.1 Concerted Additions, 156 6.2 SN2 Reactions, 158 6.3 Radical Mechanisms, 160 6.4 Ionic Mechanisms, 163 6.5 Reductive Elimination, 164 6.6 s-Bond Metathesis, 170 6.7 Oxidative Coupling and Reductive Fragmentation, 172 7 Insertion and Elimination 177 7.1 Reactions Involving CO, 179 7.2 Insertions Involving Alkenes, 185 7.3 Other Insertions, 191 7.4 a, b, g, and d Elimination, 192 8 Nucleophilic and Electrophilic Addition and Abstraction 199 8.1 Nucleophilic Addition to CO, 202 8.2 Nucleophilic Addition to Polyene and Polyenyl Ligands, 204 8.3 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls, 212 8.4 Electrophilic Addition, 213 8.5 Electrophilic Abstraction of Alkyl Groups, 216 8.6 Single-Electron Transfer Pathways, 218 8.7 Reactions of Organic Free Radicals with Metal Complexes, 219 9 Homogeneous Catalysis 225 9.1 Alkene Isomerization, 229 9.2 Alkene Hydrogenation, 231 9.3 Alkene Hydroformylation, 244 9.4 Hydrocyanation of Butadiene, 247 9.5 Alkene Hydrosilylation and Hydroboration, 250 9.6 Coupling Reactions, 252 9.7 Organometallic "Oxidase" Reactions, 254 9.8 Surface and Supported Organometallic Catalysis, 255 10 Physical Methods in Organometallic Chemistry 263 10.1 Isolation, 263 10.2 1H NMR Spectroscopy, 264 10.3 13C NMR Spectroscopy, 268 10.4 31P NMR Spectroscopy, 270 10.5 Dynamic NMR, 272 10.6 Spin Saturation Transfer, 276 10.7 T 1 and the Nuclear Overhauser Effect, 277 10.8 Isotopic Perturbation of Resonance, 280 10.9 IR Spectroscopy, 283 10.10 Crystallography, 286 10.11 Other Methods, 288 11 Metal-Ligand Multiple Bonds 296 11.1 Carbenes, 296 11.2 Carbynes, 311 11.3 Bridging Carbenes and Carbynes, 313 11.4 N -Heterocyclic Carbenes, 315 11.5 Multiple Bonds to Heteroatoms, 319 12 Applications of Organometallic Chemistry 327 12.1 Alkene Metathesis, 327 12.2 Dimerization, Oligomerization, and Polymerization of Alkenes, 334 12.3 Activation of CO and CO2, 343 12.4 C-H Activation, 348 12.5 Organometallic Materials and Polymers, 354 13 Clusters, Nanoparticles, Materials, and Surfaces 361 13.1 Cluster Structures, 362 13.2 Structures, 362 13.3 The Isolobal Analogy, 374 13.4 Nanoparticles, 378 13.5 Giant Molecules, 381 13.6 Organometallic Materials, 381 14 Applications to Organic Synthesis 388 14.1 Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond Formation, 389 14.2 Metathesis, 396 14.3 Rhodium Carbenes in Cyclopropanation and C-H Insertion, 397 14.4 Hydrogenation and Related Reactions, 399 14.5 Carbonylation, 401 14.6 Oxidation, 405 14.7 C-H Activation, 408 14.8 Click Chemistry, 412 14.9 Noncatalytic Reactions, 413 15 Paramagnetic, High-Oxidation-State, and High-Coordination-Number Complexes 421 15.1 Magnetism and Spin States, 422 15.2 Polyalkyls, 429 15.3 Polyhydrides, 434 15.4 Cyclopentadienyl Complexes, 437 15.5 f -Block Complexes, 439 16 Bioorganometallic Chemistry 448 16.1 Introduction, 448 16.2 Coenzyme B12, 454 16.3 Nitrogen Fixation, 460 16.4 Nickel Enzymes, 467 16.5 Biomedical Applications, 472 Useful Texts on Allied Topics 477 Major Reaction Types 479 Solutions to Problems 481 Index 496