The Organometallic Chemistry of the Transition Metals

ROBERT H. CRABTREE, PhD, is a professor in the Department of Chemistry at Yale University. He has served on the editorial boards of Chemical Reviews, New Journal of Chemistry, Journal of Molecular Catalysis, and Organometallics and has received numerous awards for his research accomplishments including the Organometallic Chemistry Prize of Royal Society of Chemistry (1991) and the Organometallic Chemistry Prize of the American Chemical Society (1993).

Preface.List of Abbreviations.1 Introduction.1.1 Werner Complexes.1.2 The Trans Effect.1.3 Soft Versus Hard Ligands.1.4 The Crystal Field.1.5 The Ligand Field.1.6 Back Bonding.1.7 Electroneutrality.1.8 Types of Ligand.2 General Properties of Organometallic Complexes.2.1 The 18-Electron Rule.2.2 Limitations of the 18-Electron Rule.2.3 Electron Counting in Reactions.2.4 Oxidation State.2.5 Coordination Number and Geometry.2.6 Effects of Complexation.2.7 Differences between Metals.2.8 Outer-Sphere Coordination.3 Metal Alkyls, Aryls, and Hydrides and Related sigma-Bonded Ligands. 3.1 Transition Metal Alkyls and Aryls.3.2 Related sigma-Bonded Ligands.3.3 Metal Hydride Complexes.3.4 sigma Complexes.3.5 Bond Strengths for Classical sigma-Bonding Ligands.4 Carbonyls, Phosphine Complexes, and Ligand Substitution Reactions.4.1 Metal Complexes of CO, RNC, CS, and NO.4.2 Phosphines and Related Ligands.4.3 Dissociative Substitution.4.4 Associative Mechanism.4.5 Redox Effects, the I Mechanism, and Rearrangements in Substitution.4.6 Photochemical Substitution.4.7 Steric and Solvent Effects in Substitution.5 Complexes of pi-Bound Ligands.5.1 Alkene and Alkyne Complexes.5.2 Allyl Complexes.5.3 Diene Complexes.5.4 Cyclopentadienyl Complexes.5.5 Arenes and Other Alicyclic Ligands.5.6 Metalacycles and Isoelectronic and Isolobal Replacement.5.7 Stability of Polyene and Polyenyl Complexes.6 Oxidative Addition and Reductive Elimination.6.1 Concerted Additions.6.2 SN2 Reactions.6.3 Radical Mechanisms.6.4 Ionic Mechanisms.6.5 Reductive Elimination.6.6 sigma-Bond Metathesis.6.7 Oxidative Coupling and Reductive Cleavage.7 Insertion and Elimination.7.1 Reactions Involving CO.7.2 Insertions Involving Alkenes.7.3 Other Insertions.7.4 alpha, beta, gamma, and delta Elimination.8 Nucleophilic and Electrophilic Addition and Abstraction.8.1 Nucleophilic Addition to CO.8.2 Nucleophilic Addition to Polyene and Polyenyl Ligands.8.3 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls.8.4 Electrophilic Addition.8.5 Electrophilic Abstraction of Alkyl Groups.8.6 Single-Electron Transfer Pathways.8.7 Reactions of Organic Free Radicals with Metal Complexes.9 Homogeneous Catalysis.9.1 Alkene Isomerization.9.2 Alkene Hydrogenation.9.3 Alkene Hydroformylation.9.4 Hydrocyanation of Butadiene.9.5 Alkene Hydrosilation and Hydroboration.9.6 Coupling Reactions.9.7 Surface and Supported Organometallic Catalysis.10 Physical Methods in Organometallic Chemistry.10.1 Isolation.10.2 1H NMR Spectroscopy.10.3 13C NMR Spectroscopy.10.4 31P NMR Spectroscopy.10.5 Dynamic NMR.10.6 Spin Saturation Transfer.10.7 T1 and the Nuclear Overhauser Effect.10.8 Isotopic Perturbation of Resonance.10.9 IR Spectroscopy.10.10 Crystallography.10.11 Other Methods.11 Metal-Ligand Multiple Bonds.11.1 Carbenes.11.2 Carbynes.11.3 Bridging Carbenes and Carbynes.11.4 N-Heterocyclic Carbenes.11.5 Multiple Bonds to Heteroatoms.12 Applications of Organometallic Chemistry.12.1 Alkene Metathesis.12.2 Dimerization, Oligomerization, and Polymerization of Alkenes.12.3 Activation of CO and CO2.12.4 CH Activation.12.5 Organometallic Materials and Polymers.13 Clusters and the Metal-Metal Bond.13.1 Structures.13.2 The Isolobal Analogy.13.3 Synthesis.13.4 Reactions.13.5 Giant Clusters and Nanoparticles.13.6 Giant Molecules.14 Applications to Organic Synthesis.14.1 Metal Alkyls Aryls, and Hydrides.14.2 Reduction, Oxidation, and Control of Stereochemistry.14.3 Protection and Deprotection.14.4 Reductive Elimination and Coupling Reactions.14.5 Insertion Reactions.14.6 Nucleophilic Attack on a Ligand.14.7 Heterocycles.14.8 More Complex Molecules.15 Paramagnetic, High-Oxidation-State, and High-Coordination-Number Complexes.15.1 Magnetism and Spin States.15.2 Polyalkyls.15.3 Polyhydrides.15.4 Cyclopentadienyl Complexes.15.5 f -Block Complexes.16 Bioorganometallic Chemistry.16.1 Introduction.16.2 Coenzyme B12.16.3 Nitrogen Fixation.16.4 Nickel Enzymes.16.5 Biomedical Applications.Useful Texts on Allied Topics.Major Reaction Types.Solutions to Problems.Index.