Mechanisms of Inorganic and Organometallic Reactions Volume 7, Softcover reprint of the original 1st ed. 1991

The objective of Mechanisms of Inorganic and Organometallic Reactions is to provide an ongoing critical review of the literature concerned with the mechanisms of reactions of inorganic and organometallic compounds. The main focus is on reactions in solution, although solid state and gas phase studies are included where they provide relevant mechanistic insight. Each volume covers an eighteen month literature period, and this, the seventh volume in the series, deals with papers published during July 1988 through December 1989. Where appropriate, there are references to earlier work, and also to specific sections in previous volumes. Coverage continues to span the whole area as comprehensively as possible in each volume, and although it is impossible be absolutely complete, every effort is made to include all the important for it to published work that is relevant to the elucidation of reaction mechanisms. Numerical data are reported in the units used by the original authors, and they are only converted to common units when making comparisons. The basic format of earlier volumes is retained to facilitate tracing progress over several years in a particular topic; this can now be done for more than a decade worth of research. In the last volume, ligand reactivity of both coordination and organometallic compounds were brought together in Chapter 12, and, in response to numerous positive comments from readers, this arrangement has been maintained. There have been some similar suggestions about oscillating reactions, and this topic may have a separate section in the next volume.

I. Electron Transfer Reactions.- 1. Electron Transfer: General and Theoretical.- 1.1. Overview and General Aspects of Reactions in Fluid Media.- 1.2. Electronic Coupling (Ke1).- 1.2.1. The Distance Dependence of Electron Transfer Rates.- 1.2.2. Electric and Magnetic Field Effects on Electronic Coupling and Related Problems of Photoinduced Electron Transfer.- 1.3. The Free-Energy Dependence of Electron Transfer Reactions: The “Inverted Region” Problem.- 1.4. The Effects of Solvent Dynamics.- 1.5. Metal-to-Metal and Ligand-to-Ligand Charge Transfer (“Inter-valence” Transfer).- 2. Redox Reactions between Two Metal Complexes.- 2.1. Introduction.- 2.2. Reactions of Metal Aqua and Oxo Ions.- 2.2.1. Titanium.- 2.2.2. Vanadium and Chromium.- 2.2.3. Iron.- 2.2.4. Molybdenum and Tungsten.- 2.3. Reactions of Metal Ion Complexes.- 2.3.1. Chromium.- 2.3.2. Manganese.- 2.3.3. Iron, Ruthenium, and Osmium.- 2.3.4. Cobalt and Rhodium.- 2.3.5. Nickel, Palladium, and Platinum.- 2.3.6. Copper and Silver.- 2.3.7. Technetium and Rhenium.- 2.3.8. Ytterbium.- 2.4. Reactions with Metalloproteins.- 2.4.1. Introduction.- 2.4.2. Copper Proteins.- 2.4.3. Hemoglobin and Myoglobin.- 2.4.4. Cytochromes.- 2.4.5. Iron-Sulfur Proteins.- 3. Metal-Ligand Redox Reactions.- 3.1. Introduction.- 3.2. Oxygen, Peroxide, and Other Oxygen Compounds.- 3.2.1. Dioxygen.- 3.2.2. Hydrogen Peroxide.- 3.2.3. Alkyl Hydroperoxides.- 3.3. Nitrogen Compounds and Oxyanions.- 3.3.1. Hydrazine, Azides, Hydroxylamines, and Derivatives.- 3.3.2. Oxynitrogen Compounds.- 3.3.3. Amines and Nitriles.- 3.4. Sulfur Compounds and Oxyanions.- 3.4.1. Peroxodisulfate and Peroxomonosulfate.- 3.4.2. Sulfur Dioxide and Sulfite Ions.- 3.4.3. Sulfoxides.- 3.4.4. Alkyl Sulfur Compounds.- 3.4.5. Selenium, Tellurium, and Elemental Sulfur.- 3.5. Halogen, Halides, and Halogen Oxyanions.- 3.5.1. Halogens.- 3.5.2. Halides.- 3.5.3. Oxyhalogen Compounds.- 3.6. Phosphorus, Arsenic, and Oxycompounds.- 3.6.1. Phosphorus Oxyanions.- 3.6.2. Phosphines and Arsines.- 3.7. Inorganic Radicals.- 3.8. Ascorbic Acid, Quinols, Catechols, and Diols.- 3.8.1. Ascorbic Acid.- 3.8.2. Aromatic Diols and Diones.- 3.8.3. Aromatic and Aliphatic Alcohols.- 3.9. Carboxylic Acids, Carboxylates, Carbon Dioxide, and Carbon Monoxide.- 3.9.1. Carboxylic Acids and Carboxylates.- 3.9.2. Carbon Dioxide and Carbon Monoxide.- 3.10. Alkyl Halides.- 3.11. Organic Radicals.- II. Substitution and Related Reactions.- 4. Reactions of Compounds of the Nonmetallic Elements.- 4.1. Boron.- 4.2. Carbon.- 4.3. Silicon.- 4.4. Germanium.- 4.5. Nitrogen.- 4.6. Phosphorus.- 4.7. Arsenic.- 4.8. Oxygen.- 4.9. Sulfur.- 4.10. Selenium and Tellurium.- 4.11. Halogens, Krypton, and Xenon.- 4.11.1. Fluorine.- 4.11.2. Chlorine.- 4.11.3. Bromine.- 4.11.4. Iodine.- 4.11.5. Krypton and Xenon.- 4.12. Oscillating Reactions.- 5. Substitution Reactions of Inert-Metal Complexes—Coordination Numbers 4 and 5.- 5.1. Introduction.- 5.2. Associative Ligand Exchange at Square-Planar Platinum(II).- 5.3. Associative Ligand Exchange at Square-Planar Palladium(II).- 5.4. Ligand Exchange at Platinum(II) by Dissociative Processes.- 5.5. Ligand Exchange at Nickel.- 5.6. Reactions of Planar Ir(I), Rh(I), Au(III), and Cu(II) Complexes.- 5.7. Five-Coordinate Species.- 5.8.TransEffect.- 5.9. Isomerizations.- 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. [Cr(III)(L5)X]n+1Systems (L = OH2, NH3).- 6.2.2. Cr(III)—C Bond Rupture.- 6.2.3. Amine and Other Complexes.- 6.2.4. Dechelation/Chelation Processes.- 6.2.5. Metal-Ion-Assisted Aquation.- 6.2.6. Porphyrins.- 6.3. Formation of Chromium(III) Complexes.- 6.3.1. The Nature of the Cr3+Cation in Aqueous Solution.- 6.3.2. Anation Reactions.- 6.4. Base Hydrolysis.- 6.5. Oxidation and Reduction of Cr(III) Complexes.- 6.6. Isomerization and Racemization.- 6.7. Photochemistry and Photophysics of Chromium(III) Complexes.- 6.8. The Solid State.- 6.8.1. Single-Crystal X-Ray Structures.- 6.8.2. Synthesis and Solid-State Decomposition.- 6.9. Other Oxidation States.- 6.9.1. Chromium(II).- 6.9.2. Chromium(IV).- 6.9.3. Chromium(V).- 6.9.4. Chromium(VI).- 6.10. Catalysis.- 6.11. Miscellaneous.- 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. Anation.- 7.5. Solvolysis.- 7.6. Isomerization.- 7.7. Carbonato Complexes.- 7.8. Vitamin B12 and Cobaloximes.- 8. Substitution Reactions of Inert-Metal Complexes—Coordination Numbers 6 and Above: Other Inert Centers.- 8.1. Introduction.- 8.2. Groups 5 to 7.- 8.2.1. Vanadium.- 8.2.2. Molybdenum.- 8.2.3. Tungsten.- 8.2.4. Manganese.- 8.2.5. Technetium.- 8.2.6. Rhenium.- 8.3. Iron.- 8.3.1. Penta-and Tetracyanoferrates.- 8.3.2. Iron(II)-Diimine Complexes.- 8.3.3. Other Iron(II) Complexes.- 8.3.4. Iron(III) Complexes.- 8.4. Ruthenium.- 8.4.1. Ruthenium(II).- 8.4.2. Ruthenium(III).- 8.4.3. Ruthenium(IV), Ruthenium(V), and Ruthenium(VI).- 8.5. Osmium.- 8.6. Rhodium.- 8.7. Iridium.- 8.8. Platinum(IV).- 9. Substitution Reactions of Labile Metal Complexes.- 9.1. General.- 9.2. Ligand Substitution on Complexes of Uni-and Bivalent Metal Ions.- 9.2.1. Ligand Substitution on Complexes of Alkali and Alkaline Earth Metal Ions.- 9.2.2. Ligand Substitution on Complexes of Gold(I) and Copper(I).- 9.2.3. Ligand Substitution on Complexes of Uni-and Bivalent First-Row Transition Metal Ions.- 9.2.4. Ligand Substitution on Complexes of Platinum(II) and Pal-ladium(II).- 9.2.5. Ligand Substitution on Complexes of Mercury(II).- 9.3. Ligand Substitution on Complexes of Trivalent Metal Ions and Metal Ions of Higher Valency.- 9.3.1. Ligand Substitution on Complexes of the Trivalent Main Group Metal Ions.- 9.3.2. Ligand Substitution on Complexes of the Trivalent Transition Metal Ions.- 9.3.3. Ligand Substitution on Complexes of the Trivalent Lan-thanide Ions.- 9.3.4. Ligand Substitution on Complexes of Oxo Metal Ions.- 9.4. Ligand Substitution Processes in Dimeric and Higher Oligomeric Metal Complexes.- III. Reactions of Organometallic Compounds.- 10. Substitution and Insertion Reactions.- 10.1. Substitution Reactions.- 10.1.1. Introduction.- 10.1.2. Mononuclear Complexes.- 10.1.3. Dinuclear Complexes.- 10.1.4. Trinuclear and Larger Clusters.- 10.2. Insertion Reactions.- 10.2.1. Carbon Monoxide Insertion.- 10.2.2. Other Insertions.- 11. Metal-Alkyl and Metal-Hydride Bond Formation and Fission; Oxidative Addition and Reductive Elimination.- 11.1. Introduction.- 11.2. Dihydrogen Complexes.- 11.3. Metal-Hydride Complexes.- 11.4. C—H Bond Activation.- 11.4.1. Unactivated C—H Bonds.- 11.4.2. Activated C—H Bonds.- 11.4.3. Intramolecular C—H Bonds.- 11.5. Reductive Elimination Forming Carbon-Carbon Bonds.- 11.6. Oxidative Addition and Reductive Elimination of Alkyl Halides.- 11.7. Oxidative Addition and Reductive Elimination Involving Two Metal Centers.- 12. Reactivity of Coordinated Ligands.- 12.1. Introduction.- 12.2. Cobalt Complexes.- 12.2.1. Amino Acids and Peptides.- 12.2.2. Carboxylic and Phosphate Esters.- 12.2.3. Ligand Synthesis.- 12.3. Other Metal Complexes.- 12.3.1. Introduction.- 12.3.2. Reactions of Coordinated Nitriles and Related Ligands.- 12.3.3. Nucleophilic Addition to Coordinated Carbonyls 287 12.3.4. Electrophilic Attack at Coordinated Nitrogen and Oxygen.- 12.3.5. Reactions of Coordinated Phosphorus Compounds.- 12.3.6. Reactions of Coordinated Sulfur Ligands.- 12.3.7. Reactions of Coordinated Heterocyclic Ligands.- 12.3.8. Reactions Involving Cyclometalated Ligands.- 12.4. Organometallic Compounds.- 12.4.1. Reactions with Nucleophiles.- 12.4.2. Reactions with Electrophiles.- 13. Rearrangements, Intramolecular Exchanges, andIsomerizations of Organometallic Compounds.- 13.1. Introduction.- 13.2. Mononuclear Compounds.- 13.2.1. Isomerizations and Ligand Site Exchange.- 13.2.2. Ligand Rotations about the Metal-Ligand Bond.- 13.2.3. Migration of Metal Atoms between Different Ligand Sites.- 13.2.4. Agostic Bonding and Hydrogen Atom Migrations.- 13.2.5. Internal Ligand Rearrangements.- 13.3. Dinuclear Compounds.- 13.3.1. Restricted Rotations.- 13.3.2. Carbonyl Ligand Migrations.- 13.3.3. Migration of Other Ligands between Metal Atoms.- 13.3.4. Other Exchange Reactions.- 13.4. Cluster Compounds.- 13.4.1. Rearrangements Involving the Relative Motion of Metal Atoms in a Cluster.- 13.4.2. Carbonyl Ligand Exchanges.- 13.4.3. Other Exchange Processes.- 14. Homogeneous Catalysis of Organic Reactions by Transition Metal Complexes.- 14.1. General.- 14.2. Hydrogenations.- 14.3. Hydrogen Transfer and Dehydrogenations.- 14.4. C—H Activation.- 14.5. Hydrosilylation.- 14.6. Nucleophilic Additions to C=C and C?C.- 14.7. Olefin Dimerization and Oligomerization.- 14.8. Alkyne Oligomerization.- 14.9. Metathesis.- 14.10. Olefin Polymerization.- 14.11. Alkyne Polymerizations.- 14.12. Carbonylations.- 14.12.1. Carbonylations of C=C and C?C.- 14.12.2. Carbonylation of Organic Halides.- 14.12.3. Hydroformylation.- 14.12.4. Water-Gas Shift Reactions.- 14.12.5. CO Reduction and Alcohol Carbonylation.- 14.13. Cross-Coupling Reactions.- IV. 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.- References.