Mechanisms of Inorganic and Organometallic Reactions

1. Electron Transfer Reactions.- 1. Electron Transfer: General and Theoretical.- 1.1. The Marcus-Hush Model.- 1.2. Quantum Mechanics of Electron Transfer.- 1.2.1. Nonadiabaticity.- 1.2.2. Nuclear Tunneling.- 1.2.3. Tunneling in the Inverted Region.- 1.2.4. Isotope Effects.- 1.2.5. Bridging Groups and Long-Range Transfer.- 1.2.6. Electron Transfer in the Gas Phase.- 1.3. Mixed-Valence Complexes.- 1.3.1. Binuclear Systems.- 1.3.2. Polynuclear Systems.- 1.3.3. Other Mixed-Valence Materials.- 1.3.4. Electrical Conductivity of Solids.- 2. Redox Reactions between Metal Complexes.- 2.1. Introduction.- 2.2. Intramolecular Electron Transfer.- 2.2.1. Inert Systems.- 2.2.2. Labile Systems.- 2.3. Titanium(III).- 2.4. Chromium(II).- 2.5. Cage Complexes.- 2.6. Iron(II).- 2.7. Copper(III), Nickel(III), and Nickel(IV).- 2.8. Copper(II)/(I).- 2.9. Ruthenium(II).- 2.10. Cobalt(I) and Rhodium(I)/(II).- 2.11. Cyano Complexes.- 2.12. Volumes of Activation.- 2.13. Stereoselectivity in Electron Transfer.- 2.14. Miscellaneous Reactions.- 2.15. Reactions of Metalloproteins.- 3. Metal-Ligand Redox Reactions.- 3.1. Introduction.- 3.2. Nitrogen Compounds and Oxoanions.- 3.2.1. Nitrate.- 3.2.2. Hydroxylamine and Hydrazine.- 3.2.3. Nitrite.- 3.2.4. Azide.- 3.2.5. Organic Amines.- 3.3. Oxygen, Peroxides, and Other Oxygen Compounds.- 3.3.1. Oxygen.- 3.3.2. Hydrogen Peroxide and Hydroperoxides.- 3.3.3. Other Oxygen Compounds.- 3.4. Halides, Halogens, and Their Oxoacids.- 3.4.1. Halogens.- 3.4.2. Halides.- 3.4.3. Hypohalites.- 3.4.4. Halates.- 3.4.5. Perhalates.- 3.5. Sulfur Compounds and Oxoacids.- 3.5.1. Thiocyanate.- 3.5.2. Dithionite.- 3.5.3. Dimethyl Sulfoxide.- 3.5.4. Peroxodisulfate.- 3.5.5. Sulfite.- 3.5.6. Thiosulfate.- 3.5.7. Thiols.- 3.6. Oxoanions of Phosphorus and Arsenic.- 3.6.1. Hypophosphite.- 3.6.2. Arsenite.- 3.6.3. Peroxodiphosphate.- 3.7. Inorganic Radicals.- 3.7.1. Kinetics.- 3.7.2. Detection of Radicals.- 3.8. Hydrogen.- 3.9. Alkyl Halides.- 3.10. Quinols, Catechols, Diols, and Alcohols.- 3.10.1 Hydroquinone and Catechol.- 3.10.2. Diols.- 3.10.3. Alcohols.- 3.11. Ascorbic Acid.- 3.12. Organic Radicals.- 3.12.1. Reactions.- 3.12.2. Formation.- 3.13. Carboxylic Acids, Carboxylates, and Carbonyl Compounds.- 3.13.1. Carboxylic Acids.- 3.13.2. Carboxylates.- 3.13.3. Carbonyl Compounds.- 3.14. Alkanes, Alkenes, Alkynes, and Arenes.- 3.14.1. Alkanes.- 3.14.2. Alkenes.- 3.14.3. Arenes.- 2: Substitution and Related Reactions.- 4. Reactions of Compounds of the Nonmetallic Elements.- 4.1. Introduction.- 4.2. Boron.- 4.3. Carbon.- 4.4. Silicon.- 4.5. Germanium.- 4.6. Nitrogen.- 4.6.1. Nitric acid, Nitration, and Nitrate Esters.- 4.6.2. Dinitrogen Tetroxide.- 4.6.3. Nitrous Acid, Nitrite Esters, Nitrosation, and Related Topics.- 4.6.4. Hydroxylamine and Nitroamine.- 4.6.5. Haloamines.- 4.6.6. Other Systems.- 4.7. Phosphorus.- 4.8. Arsenic and Antimony.- 4.9. Oxygen.- 4.10. Sulfur.- 4.11. Selenium and Tellurium.- 4.12. Halogens.- 4.12.1. Fluorine.- 4.12.2. Chlorine.- 4.12.3. Bromine.- 4.12.4. Iodine.- 4.12.5. Oscillating Reactions.- 5. Substitution Reactions of Inert-Metal Complexes— Coordination Numbers 4 and 5.- 5.1. Introduction.- 5.2. Substitution at Square-Planar Complexes.- 5.2.1. General.- 5.2.2. Anation Reactions.- 5.2.3. Chelate Complexes.- 5.3. Cis and Trans Effects.- 5.4. Five-Coordinate Complexes.- 5.5. Isomerization Reactions.- 5.6. Miscellaneous.- 6. Substitution Reactions of Inert-Metal Complexes— Coordination Numbers 6 and Above: Chromium.- 6.1. Introduction.- 6.2. Aquation and Solvolysis of Chromium(III) Complexes.- 6.2.1. Unidentate Leaving Groups.- 6.2.2. Multidentate Leaving Groups.- 6.2.3. Bridged Dichromium(III) Complexes.- 6.3. Formation of Chromium(III) Complexes.- 6.3.1. Reactions of [Cr(H20)6]3+.- 6.3.2. Formation of Mixed-Ligand Complexes.- 6.4. Chromium(III) Photochemistry.- 6.5. Isomerization and Racemization Reactions.- 6.6. Base Hydrolysis of Chromium(III) Complexes.- 6.7. Solids.- 6.8. Other Chromium Oxidation States.- 6.8.1. Chromium(I).- 6.8.2. Chromium(II).- 6.8.3. Chromium(V) and Chromium(VI).- 7. Substitution Reactions of Inert-Metal Complexes— Coordination Numbers 6 and Above: Cobalt.- 7.1. Aquation.- 7.2. Catalyzed Aquation.- 7.3. Base Hydrolysis.- 7.4. Solvolysis.- 7.5. Anation.- 7.6. Solvent Exchange, Racemization, Isomerization, and Ligand Exchange.- 7.7. Decarboxylation of Carbonato Complexes in Acidic Solution.- 7.8. Formation.- 7.9. Photochemistry.- 7.10. Reactions of Coordinated Ligands.- 7.10.1. Nitrile Hydrolysis.- 7.10.2. Amino Acid Synthesis.- 7.10.3. Peptide Synthesis.- 7.10.4. Imine Formation.- 7.10.5. Base-Catalyzed Exchange Reactions.- 7.10.6. Phosphato Complexes.- 7.10.7. B12 and B12 Models.- 7.10.8. Ligand Oxidation.- 8. Substitution Reactions of Inert-Metal Complexes— Coordination Numbers 6 and Above: Other Inert Centers.- 8.1. Groups VI and VII.- 8.1.1. Molybdenum.- 8.1.2. Technetium.- 8.2. Iron.- 8.2.1. Pentacyanoferrates(II).- 8.2.2. Iron(II)-Diimine Complexes.- 8.2.3. Other Low-Spin Iron(II) Complexes.- 9.2.4. Iron(III) Complexes.- 8.3. Ruthenium.- 8.3.1. Ruthenium(II).- 8.3.2. Ruthenium(III).- 8.4. Osmium.- 8.5. Rhodium.- 8.5.1. Aquation.- 8.5.2. Base Hydrolysis.- 8.5.3. Catalyzed Aquation.- 8.5.4. Formation.- 8.5.5. Solvent Exchange.- 8.5.6. Ligand Replacement.- 8.5.7. Ring Opening and Closing.- 8.5.8. Isomerization.- 8.5.9. Photochemistry.- 8.5.10. Reactions of Coordinated Ligands.- 8.6. Iridium.- 8.7. Platinum(IV).- 8.7.1. General.- 8.7.2. Isomerization at Coordinated Sulfur or Selenium.- 9. Substitution Reactions of Labile Metal Complexes.- 9.1. Complex Formation Involving Unsubstituted Metal Ions: Unidentate Ligands and Solvent Exchange.- 9.1.1. Bivalent Ions.- 9.1.2. Ions of Valency Three and Higher.- 9.2. Complex Formation Involving Unsubstituted Metal Ions: Multidentate Ligands.- 9.2.1. Univalent Ions.- 9.2.2. Bivalent Ions.- 9.2.3. Ions of Valency Three and Higher.- 9.3. The Effects of Bound Ligands.- 9.3.1. Reactions in Water.- 9.3.2. Reactions in Nonaqueous Solvents.- 3. Reactions of Organometallic Compounds.- 10. Substitution and Insertion Reactions of Organometallic Compounds.- 10.1. Substitution Reactions.- 10.1.1. Introduction.- 10.1.2. Substitution in 17-Electron Mononuclear Complexes.- 10.1.3. Substitution in Other Mononuclear Complexes.- 10.1.4. Substitution in Polynuclear Complexes.- 10.2. Insertion Reactions.- 10.2.1. Carbon Monoxide Insertion.- 10.2.2. Alkene, Alkyne, and Carbene Insertion.- 10.2.3. Insertion of Other Groups.- 11. Metal-Alkyl Bond Formation and Fission; Oxidative Addition and Reductive Elimination.- 11.1. Introduction.- 11.2. Metal-Alkyl Bonds.- 11.2.1. Chromium.- 11.2.2. Cobalt.- 11.2.3. Lithium.- 11.2.4. Germanium and Silicon.- 11.2.5. Yttrium and Titanium.- 11.2.6. Tantalum.- 11.2.7. Manganese.- 11.2.8. Iron, Cobalt, and Nickel.- 11.2.9. Rhodium.- 11.2.10. Palladium and Platinum.- 11.2.11. Gold, Mercury, Thallium, and Tin.- 11.2.12. Lutetium.- 11.2.13. Thorium.- 11.3. Oxidative Addition and Reductive Elimination.- 11.3.1. Magnesium.- 11.3.2. Gallium and Indium.- 11.3.3. Silicon.- 11.3.4. Titanium, Zirconium, and Hafnium.- 11.3.5. Tantalum.- 11.3.6. Chromium, Molybdenum, and Tungsten.- 11.3.7. Manganese and Rhenium.- 11.3.8. Iron, Ruthenium, and Osmium.- 11.3.9. Gas-Phase Reactions of Fe+, Co+, Ni+, and Rh+.- 11.3.10. Cobalt.- 11.3.11. Rhodium.- 11.3.12. Iridium.- 11.3.13. Nickel.- 11.3.14. Palladium.- 11.3.15. Platinum.- 11.3.16. Gold and Mercury.- 11.3.17. Actinides.- 12. Reactivity of Coordinated Hydrocarbons.- 12.1. Introduction.- 12.2. Nucleophilic Addition and Substitution.- 12.2.1. (?-Bonded Hydrocarbons.- 12.2.2. ?-Bonded Hydrocarbons.- 12.2.3. Reactions at Side Chains and Exocyclic Carbocations.- 12.2.4. Attack at Isocyanide Ligands.- 12.3. Electrophilic Attack.- 12.4. Miscellaneous Reactions.- 13. Rearrangements, Intramolecular Exchanges, and Isomerization of Organometallic Compounds.- 13.1. Mononuclear Compounds.- 13.1.1. Isomerizations and Ligand Site Exchange.- 13.1.2. Simple Ligand Rotation about the Metal-Ligand Axis.- 13.1.3. Migration of Metal Atoms between Different Ligand Sites.- 13.1.4. Hydrogen Atom Transfer Reactions.- 13.2. Dinuclear Compounds.- 13.2.1. Carbonyl Ligand Exchange.- 13.2.2. Transfer of Other Ligands between Metal Atoms.- 13.2.3. Bridge-Terminal Ligand Exchange.- 13.2.4. Bridging Alkyne Rotation.- 13.3. Cluster Compounds.- 13.3.1. Rearrangements Involving the Relative Motion of Metal Atoms in a Cluster.- 13.3.2. Localized Carbonyl Exchange.- 13.3.3. Delocalized Carbonyl Exchange.- 13.3.4. Hydride Exchange.- 13.3.5. Organic Ligand Mobility.- 14. Homogeneous Catalysis of Organic Reactions by Complexes of Metal Ions.- 14.1. Introduction.- 14.1.1. General Reviews and Elementary Steps in Homogeneous Catalysis.- 14.2. Reactions Involving Carbon Monoxide.- 14.2.1. Hydroformylation and Hydrocarboxylation of Olefins.- 14.2.2. Carbonylation and Homologation of Alcohols, Ethers, Alkyl Halides, and Carboxylic Esters.- 14.2.3. Fischer-Tropsch Reactions.- 14.2.4. The Homogeneous Water-Gas Shift Reaction (WGSR).- 14.3. Oxidation.- 14.4. Hydrogenation.- 14.4.1. Hydrogenation of Alkenes;.- 14.4.2. Hydrogenation of Arenes and Ketones.- 14.4.3. Asymmetric Hydrogenation.- 14.4.4. Hydrogen Transfer and Dehydrogenation Reactions.- 14.5. Skeletal Rearrangements.- 14.6. Metathesis Reactions.- 14.6.1. Alkene and Alkyne Metathesis.- 14.6.2. Amine Disproportionate.- 14.7. Oligomerization and Polymerization of Alkenes and Alkynes.- 14.7.1. Reactions of Alkenes.- 14.7.2. Reactions of Alkynes.- 14.8. Reactions of Dinitrogen.- 4. Compilations of Numerical Data.- 15. Volumes of Activation for Inorganic and Organometallic Reactions: A Tabulated Compilation.- 15.1. Introduction.- 15.2. Data in Tabular Form.- Abbreviations Used in the Tables.- References.- Author Index.