The Organometallic Chemistry of the Transition Metals

Contents Acknowledgment List of Abbreviations Periodic Table 1 Introduction 1.1 Why Study Organometallic Chemistry? 1.2 Coordination Chemistry 1.3 Werner Complexes 1.4 The Trans Effect 1.5 Soft versus Hard Ligands 1.6 The Crystal Field 1.7 The Ligand Field 1.8 Two Electron-Three Center Bonding 1.9 Four Electron-Three Center Bonding 1.10 Back Bonding 1.11 Trends in d Orbital Energies 1.12 Types of Ligand References Problems 2 Making Sense of Organometallics 2.1 The 18-Electron Rule 2.2 Limitations of the 18-Electron Rule 2.3 Electron Counting in Reactions 2.4 The Oxidation State Concept and its Limitations 2.5 Electroneutrality 2.6 Coordination Number and Geometry 2.7 Effects of Complexation 2.8 Differences between Metals References Problems 3 Alkyls and Hydrides 3.1 Alkyls and Aryls 3.2 Others-bonded Ligands 3.3 Metal Hydrides 3.4 Sigma Complexes 3.5 Bond Strengths References Problems 4 Ligand Substitution 4.1 Metal Carbonyls 4.2 Phosphines 4.3 N-Heterocyclic Carbenes 4.4 Dissociative Substitution 4.5 Associative Substitution 4.6 Redox Effects and Interchange Substitution 4.7 Photochemical Substitution 4.8 Counterions and Solvents in Substitution References Problems 5 Pi-Complexes 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 5.7 Stability of Polyene and Polyenyl Complexes References Problems 6 Oxidative Addition and Reductive Elimination 6.1 Introduction 6.2 Concerted Additions 6.3 SN2 Pathways 6.4 Radical Mechanisms 6.5 Ionic Mechanisms 6.6 Reductive Elimination 6.7 Sigma Bond Metathesis 6.8 Ligand-Assisted 12-Additions and Eliminations 6.9 Oxidative Coupling 6.10 Proton Coupled Electron Transfer References Problems 7 Insertion and Elimination 7.1 Introduction 7.2 11-Insertion 7.3 12-Insertion 7.4 Outer Sphere Insertions 7.5 a b g and d Elimination References Problems 8 Addition and Abstraction 8.1 Introduction 8.2 Nucleophilic Addition to CO 8.3 Nucleophilic Addition to Polyene and Polyenyls 8.4 Nucleophilic Abstraction 8.5 Electrophilic Addition and Abstraction 8.6 Single-Electron Transfer and Radical Reactions References Problems 9 Homogeneous Catalysis 9.1 Catalytic Cycles 9.2 Alkene Isomerization 9.3 Hydrogenation 9.4 Alkene Hydroformylation 9.5 Alkene Hydrocyanation 9.6 Alkene Hydrosilylation 9.7 Coupling Reactions 9.8 Organometallic Oxidation Catalysis 9.9 Electrocatalysis 9.10 Photoredox Catalysis 9.11 Surface Supported Single Atom and Cooperative Catalysis References Problems 10 Physical Methods 10.1 Mechanism 10.2 H NMR Spectroscopy 10.3 C NMR Spectroscopy 10.4 P NMR Spectroscopy 10.5 Dynamic NMR 10.6 Spin Saturation Transfer 10.7 T1 and the Nuclear Overhauser Effect 10.8 IR Spectroscopy 10.9 Crystallography 10.10 Electrochemistry and EPR 10.11 Computation 10.12 Other Methods References Problems 11 M-L 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 References Problems 12 Metathesis Polymerization and Bond Activation 12.1 Alkene Metathesis 12.2 Alkene Dimerization Oligomerization and Polymerization 12.3 Activation of CO and CO2 12.4 C-H Activation 12.5 Dehydrogenative Oxidation and Hydrogen Borrowing References Problems 13 Green Energy & Materials Applications 13.1 Green Chemistry 13.2 Energy Chemistry 13.3 Clusters and Nanoparticles 13.4 Organometallic Materials References Problems 14 Organic Applications 14.1 Carbon-Carbon and Carbon-Heteroatom Coupling 14.2 Metathesis 14.3 Cyclopropanation and C-H Insertion 14.4 Hydrogenation 14.5 Carbonylation 14.6 Oxidation 14.7 C-H Activation 14.8 Click Chemistry and Cycloaddition 14.9 Photoredox Catalysis References Problems 15 Paramagnetic and High-Oxidation-State Complexes 15.1 Magnetism and Spin States 15.2 Cyclopentadienyl Complexes 15.3 f-Block Complexes References Problems 16 Bioorganometallic Chemistry 16.1 Introduction 16.2 Coenzyme B12 16.3 Nitrogen Fixation 16.4 Nickel Enzymes 16.5 Artificial Enzymes 16.6 Biomedical and Biocatalytic Applications References Problems Useful Texts on Allied Topics Major Reaction Types Solutions to Problems Index 000