The Organometallic Chemistry of the Transition Metals

ISBN-13: 9781119465881 / Angielski / Twarda / 2019 / 464 str.

Robert H. Crabtree

Spis treści

Preface xiAcknowledgments xiiiList of Abbreviations xv1 Introduction 11.1 Why Study Organometallic Chemistry? 11.2 Coordination Chemistry 31.3 Werner Complexes 31.4 The Trans Effect 71.5 Soft Versus Hard Ligands 91.6 The Crystal Field 101.7 The Ligand Field 171.8 Two-Electron Three-Center Bonding 191.9 Four-Electron Three-Center Bonding 201.10 Back Bonding 221.11 Trends in d Orbital Energies 261.12 Types of Ligand 27References 32Problems 332 Making Sense of Organometallics 352.1 The 18-Electron Rule 352.2 Limitations of the 18-Electron Rule 432.3 Electron Counting in Reactions 452.4 The Oxidation State Concept and its Limitations 462.5 Electroneutrality 522.6 Coordination Number and Geometry 532.7 Effects of Complexation 562.8 Differences between Metals 58References 62Problems 633 Alkyls and Hydrides 653.1 Alkyls and Aryls 653.2 Other sigma-Bonded Ligands 793.3 Metal Hydrides 803.4 Sigma Complexes 833.5 Bond Strengths 86References 88Problems 894 Ligand Substitution 914.1 Metal Carbonyls 914.2 Phosphines 1004.3 N-Heterocyclic Carbenes 1034.4 Dissociative Substitution 1054.5 Associative Substitution 1094.6 Redox Effects and Interchange Substitution 1114.7 Photochemical Substitution 1134.8 Counterions and Solvents in Substitution 115References 116Problems 1185 Pi Complexes 1215.1 Alkene and Alkyne Complexes 1215.2 Allyl Complexes 1265.3 Diene Complexes 1305.4 Cyclopentadienyl Complexes 1335.5 Arenes and Other Alicyclic Ligands 1405.6 Metalacycles 1435.7 Stability of Polyene and Polyenyl Complexes 144References 145Problems 1456 Oxidative Addition and Reductive Elimination 1476.1 Introduction 1476.2 Concerted Additions 1496.3 SN2 Pathways 1526.4 Radical Mechanisms 1536.5 Ionic Mechanisms 1556.6 Reductive Elimination 1566.7 Sigma Bond Metathesis 1626.8 Ligand-Assisted 1,2-Additions and Eliminations 1636.9 Oxidative Coupling 1646.10 Proton-Coupled Electron Transfer 165References 166Problems 1677 Insertion and Elimination 1697.1 Introduction 1697.2 1,1-Insertion 1717.3 1,2-Insertion 1757.4 Outer Sphere Insertions 1797.5 alpha-,ß-,gamma- and delta-Elimination 180References 182Problems 1828 Addition and Abstraction 1858.1 Introduction 1858.2 Nucleophilic Addition to CO 1878.3 Nucleophilic Addition to Polyenes and Polyenyls 1898.4 Nucleophilic Abstraction 1968.5 Electrophilic Addition and Abstraction 1978.6 Single-Electron Transfer and Radical Reactions 200References 201Problems 2029 Homogeneous Catalysis 2059.1 Catalytic Cycles 2059.2 Alkene Isomerization 2119.3 Hydrogenation 2139.4 Alkene Hydroformylation 2219.5 Alkene Hydrocyanation 2239.6 Alkene Hydrosilylation 2249.7 Coupling Reactions 2259.8 Organometallic Oxidation Catalysis 2279.9 Electrocatalysis 2299.10 Photoredox Catalysis 2299.11 Surface Supported Single-Atom and Cooperative Catalysis 231References 233Problems 23510 Physical Methods 23910.1 Mechanism 23910.2 1H NMR Spectroscopy 24010.3 13C NMR Spectroscopy 24310.4 31P NMR Spectroscopy 24410.5 Dynamic NMR 24610.6 Spin Saturation Transfer 24910.7 T1 and the Nuclear Overhauser Effect 25010.8 IR Spectroscopy 25410.9 Crystallography 25610.10 Electrochemistry and EPR 25710.11 Computation 25910.12 Other Methods 260References 262Problems 26311 M-L Multiple Bonds 26511.1 Carbenes 26511.2 Schrock Carbenes 27211.3 Carbynes 27611.4 Bridging Carbenes and Carbynes 27811.5 N-Heterocyclic Carbenes 27911.6 Multiple Bonds to Heteroatoms 282References 285Problems 28612 Metathesis Polymerization and Bond Activation 28912.1 Alkene Metathesis 28912.2 Alkene Dimerization, Oligomerization, and Polymerization 29512.3 Activation of CO and CO2 30112.4 C.H Activation 30512.5 Dehydrogenative Oxidation and Hydrogen Borrowing 309References 311Problems 31313 Green Energy and Materials Applications 31713.1 Green Chemistry 31713.2 Energy Chemistry 32013.3 Clusters and Nanoparticles 32313.4 Organometallic Materials 325References 332Problems 33414 Organic Applications 33714.1 Carbon-Carbon and Carbon-Heteroatom Coupling 33814.2 Metathesis 34314.3 Cyclopropanation and C-H Insertion 34514.4 Hydrogenation 34614.5 Carbonylation 34814.6 Oxidation 35014.7 C-H Activation 35214.8 Click Chemistry and Cycloaddition 35514.9 Photoredox Catalysis 356References 359Problems 36015 Paramagnetic and High-Oxidation-State Complexes 36315.1 Magnetism and Spin States 36415.2 Cyclopentadienyl Complexes 37115.3 f-Block Complexes 373References 380Problems 38116 Bioorganometallic Chemistry 38316.1 Introduction 38416.2 Coenzyme B12 38816.3 Nitrogen Fixation 39416.4 Nickel Enzymes 40216.5 Artificial Enzymes 40716.6 Biomedical and Biocatalytic Applications 407References 410Problems 412Appendix A: Useful Texts on Allied Topics 415Appendix B: Major Reaction Types 419Solutions to Problems 421Index 437

O autorze

Robert H. Crabtree F.R.S. is Whitehead Professor of Chemistry at Yale, a Fellow of the Royal Society and of the American Chemical Society, and a member of the American Academy and of the National Academy of Sciences.