Mechanisms of Inorganic and Organometallic Reactions

1. Electron Transfer Reactions.- 1. General Redox Processes and Reactions between Two Complexes.- 1.1. Introduction.- 1.2. General Background.- 1.2.1. General and Theoretical.- 1.2.2. Theoretical Developments.- 1.2.3. Optical Electron Transfer.- 1.3. Reaction Mechanisms.- 1.3.1. Inner-Sphere and Outer-Sphere Reactions.- 1.3.2. Solvent Effects in Electron Transfer Reactions.- 1.4. Excited State Electron Transfer.- 1.5. Stereoselectivity in Electron Transfer.- 1.6. Metalloprotein Redox Reactions.- 2. Metal-Ion-Ligand Redox Reactions.- 2.1. Introduction.- 2.2. Metal Complexes with Inorganic Substrates.- 2.2.1. Reactions of Hydrazine and Hydroxylamine.- 2.2.2. Reactions of Nitrate and Nitrite.- 2.2.3. Reactions of Thiocyanate.- 2.2.4. Reactions of Dithionite and Thiosulfate.- 2.2.5. Reactions of Iodide.- 2.2.6. Other Reductants.- 2.3. Oxidation of Organic Substrates by Metal Ion Complexes.- 2.3.1. Chromium(VI).- 2.3.2. Vanadium(V).- 2.3.3. Manganese(III) and Manganese(VII).- 2.3.4. Iron(III).- 2.3.5. Thallium(III).- 2.3.6. Iridium(IV).- 2.3.7. Cerium(IV).- 2.3.8. Cobalt(III).- 2.3.9. Bromate.- 2.3.10. Other Oxidizing Agents.- 2.4. Oxidation of Metal Ion Complexes.- 2.4.1. Iron(II).- 2.4.2. Chromium(II).- 2.4.3. Vanadium(II).- 2.4.4. Cobalt(II).- 2.4.5. Other Reductants.- 2.5. Intramolecular Electron Transfer.- 2. Substitution and Related Reactions.- 3. Reactions of Compounds of the Nonmetallic Elements.- 3.1. Introduction.- 3.2. Boron.- 3.3. Group IV Elements.- 3.3.1. Carbon.- 3.3.2. Silicon.- 3.3.3. Germanium.- 3.4. Group V Elements.- 3.4.1. Nitrogen.- 3.4.2. Phosphorus.- 3.4.3. Arsenic.- 3.4.4. Antimony.- 3.5. Group VI Elements.- 3.5.1. Oxygen.- 3.5.2. Sulfur.- 3.5.3. Selenium.- 3.5.4. Tellurium.- 3.6. Group VII Elements.- 3.6.1. Fluorine.- 3.6.2. Chlorine.- 3.6.3. Bromine.- 3.6.4. Iodine.- 4. Substitution Reactions of Inert Metal Complexes- Coordination Numbers 4 and 5.- 4.1. Introduction.- 4.2. Square-Planar Complexes.- 4.2.1. Platinum(II).- 4.2.2. Palladium(II).- 4.2.3. Nickel(II).- 4.2.4. Gold(III).- 4.2.5. Miscellaneous.- 4.2.6. Isomerization.- 4.3. Tetrahedral Complexes.- 4.4. Five-Coordinate Complexes.- 5. Substitution Reactions of Inert Metal Complexes-Coordination Numbers 6 and Above.- 5.1. Introduction.- 5.2. Chromium.- 5.2.1. Introduction.- 5.2.2. Aquation and Solvolysis of Chromium(III) Complexes.- 5.2.3. Formation of Chromium(III) Complexes.- 5.2.4. Chromium(III) Photochemistry.- 5.2.5. Isomerization and Racemization Reactions.- 5.2.6. Base Hydrolysis.- 5.2.7. Solids.- 5.2.8. Other Chromium Oxidation States.- 5.3. Group VII Elements.- 5.3.1. Technetium.- 5.3.2. Rhenium.- 5.4. Iron.- 5.4.1. Pentacyanoferrate(II) Complexes.- 5.4.2. Diimine Complexes.- 5.4.3. Other Low-Spin Iron(II) Complexes.- 5.4.4. Iron(III) Complexes.- 5.5. Ruthenium.- 5.5.1. Ruthenium(II).- 5.5.2. Ruthenium (III).- 5.5.3. Ruthenium(IV).- 5.6. Osmium.- 5.7. Cobalt(III).- 5.7.1. Aquation and Solvolysis.- 5.7.2. Base Hydrolysis and Base Solvolysis.- 5.7.3. Catalyzed Aquation.- 5.7.4. Formation.- 5.7.5. Solvent and Ligand Exchange.- 5.7.6. Racemization and Isomerization.- 5.7.7. Carbonate and Sulfite Complexes.- 5.7.8. Bis(glyoximato) Complexes.- 5.7.9. ?-Dicobalt(III) Complexes.- 5.7.10. Photochemistry.- 5.7.11. Reactions of Coordinated Ligands.- 5.8. Rhodium(III).- 5.8.1. Aquation.- 5.8.2. Base Hydrolysis.- 5.8.3. Catalyzed Aquation.- 5.8.4. Formation.- 5.8.5. Solvent and Ligand Exchange.- 5.8.6. Ring Opening and Closing.- 5.8.7. Isomerization.- 5.8.8. Carbonate and Sulfite Complexes.- 5.8.9. Bis(glyoximato) Complexes.- 5.8.10. Photochemistry.- 5.9. Iridium.- 5.9.1. Iridium(III).- 5.9.2. Iridium(IV).- 5.10. Platinum(IV).- 5.10.1. General.- 5.10.2. Inversion at Coordinated Sulfur and Selenium.- 6. Substitution Reactions of Labile Metal Complexes.- 6.1. Complex Formation Involving Unsubstituted Metal Ions with Unidentate Ligands and Solvent Exchange.- 6.1.1. Univalent Ions.- 6.1.2. Bivalent Ions.- 6.1.3. Ions of Valency 3 and Higher.- 6.2. Complex Formation Involving Unsubstituted Metal Ions and Multidentate Ligands.- 6.2.1. Univalent Ions.- 6.2.2. Bivalent Ions.- 6.2.3. Ions of Valency 3 and Higher.- 6.3. The Effects of Bound Ligands.- 6.3.1. Reactions in Water.- 6.3.2. Reactions in Nonaqueous Solvents.- 3. Reactions of Organometallic Compounds.- 7. Metal-Alkyl Bond Fission and Formation.- 7.1. Introduction.- 7.2. Metal-Alkyl Bond Fission.- 7.3. Miscellaneous Thermal Decompositions.- 7.4. Metal-Alkyl Bond Formation.- 7.5. Transalkylation.- 8. Substitution, Oxidative Addition-Reductive Elimination, and Migration-Insertion Reactions.- 8.1. Introduction.- 8.2. Substitution Reactions.- 8.2.1. Reactions Involving Carbonyls or Carbon Monoxide.- 8.2.2. Reactions Involving Di- or Multihapto Ligands.- 8.3. Oxidative Addition and Reductive Elimination.- 8.4. Migration-Insertion Reactions.- 9. Rearrangements, Intramolecular Exchanges, and Isomerization of Organometallic Compounds.- 9.1. Mononuclear Compounds.- 9.1.1. Isomerizations and Intramolecular Exchanges.- 9.1.2. Simple Ligand Rotation at a Metal Center.- 9.1.3. Ligand Motion Involving Changes in Hapiticity.- 9.1.4. Metal Migration between Different Ligand Sites.- 9.1.5. Hydrogen Migrations Involving Hydrogen Bound to Carbon.- 9.1.6. Alkyl Migration Reactions.- 9.1.7. Intraligand Rotations and Rearrangements.- 9.2. Dinuclear Compounds.- 9.2.1. Migration of CO and Related Ligands.- 9.2.2. Hydrogen Migration Reactions.- 9.2.3. Motion Involving Bridging Organic Ligands.- 9.2.4. Rotation about Metal-Metal Bonds.- 9.3. Cluster Compounds.- 9.3.1. Fluxional Metal Frameworks.- 9.3.2. Migration of CO and Related Ligands.- 9.3.3. Hydrogen Migration Reactions.- 9.3.4. Motion Involving Bridging Organic Ligands.- 10. Reactivity of Coordinated Hydrocarbons.- 10.1. Introduction.- 10.2. Nucleophilic Addition and Substitution.- 10.2.1. ?-Bonded Hydrocarbons.- 10.2.2. ?-Bonded Hydrocarbons.- 10.2.3. Reactions at Side Chains and Exocyclic Carbocations.- 10.2.4. Attack at Carbonyl Ligands.- 10.3. Electrophilic Attack.- 11. Homogeneous Catalysis of Organic Reactions by Complexes of Metal Ions.- 11.1. Introduction.- 11.1.1. Scope of the Review.- 11.1.2. Elementary Steps in Homogeneous Catalysis.- 11.2. Reactions Catalyzed by Carbene Complexes.- 11.2.1. Alkene Metathesis.- 11.2.2. Ring-Opening Polymerization by Metallocarbene Complexes.- 11.3. Hydrogenation.- 11.3.1. Introduction.- 11.3.2. Hydrogenation of Alkenes.- 11.3.3. Asymmetric Hydrogenation.- 11.3.4. Hydrogenation of Aromatic Hydrocarbons.- 11.3.5. Hydrogen Transfer Hydrogenation.- 11.4. Reactions of Carbon Monoxide.- 11.4.1. Hydroformylation.- 11.4.2. Carbonylation of Alcohols.- 11.4.3. The Homogeneous Water Gas Shift Reaction (WGSR).- 11.5. Oxidation.- References.- Author Index.- General Subject Index.