Mechanisms of Inorganic and Organometallic Reactions : Volume 6

This series, Mechanisms of Inorganic and Organometallic Reactions, provides an ongoing critical review of the published literature concerned with the mechanisms of reactions of inorganic and organometallic compounds. Emphasis is on reactions in solution, although solid state and gas phase studies are included where they provide mechanistic insight. The sixth volume deals with papers published during the period January 1987 through June 1988 inclusive, together with some earlier work where it is appropriate to make comparisons. Coverage spans the whole area as comprehensively as practically possible, and the cited references are chosen for their relevance to the elucidation of reaction mechanisms. The now familiar format of earlier volumes has been maintained to facilitate tracing progress in a particular topic over several volumes, but some small changes have been made. Reflecting the a'mount of mechanistic work associated with ligand reactivity, and the growing importance of this area, Chapter 12 has been renamed and enlarged to bring together informa­ tion on both coordination and organometallic systems involving ligand reactions. Numerical data are usually reported in the units used by the original authors, except when making comparisons and conversion to common units is necessary.

I. Electron Transfer Reactions.- 1. Electron Transfer: General and Theoretical.- 1.1. Overview of Reactions in Fluid Media.- 1.2. The Electronic Coupling Problem (Ke/).- 1.2.1. The Distance Dependence of Electron Transfer Rates.- 1.2.2. The “Inverted Region”.- 1.2.3. Related Excited-State Energy-Transfer Processes.- 1.3. Medium Effects: Thermodynamic.- 1.4. Medium Effects: Kinetic.- 1.4.1. Conformational Effects.- 1.4.2. Slow and Fast Solvation: Theory.- 1.4.3. Effects of “Slow” Solvent Relaxation Processes.- 1.4.4. Effects of “Fast” Solvent Relaxation Processes.- 1.5. Optical Electron Transfer (Intervalence Transitions).- 1.5.1. Medium Effects on Intervalence Charge Transfer.- 1.6. Charge-Transfer Excited-State Relaxation and Excited State Reactions.- 1.7. Gas Phase Reactions.- 1.7.1. Atom-Atom Reactions.- 1.7.2. Reactions Involving Molecules.- 1.8. Electron Transfer in the Solid State.- 2. Redox Reactions between Two Metal Complexes.- 2.1. Introduction.- 2.2. Reactions of Metal Aqua and Oxo Ions.- 2.2.1. Titanium(III) and (IV).- 2.2.2. Vanadium(IV) and (V).- 2.2.3. Chromium(II).- 2.2.4. Manganese(VI).- 2.2.5. Iron(II) and Ruthenium(II).- 2.2.6. Uranium(IV) and (VI).- 2.2.7. Miscellaneous Reactions.- 2.3. Reactions of Metal Ion Complexes.- 2.3.1. Manganese(III).- 2.3.2. Iron(II) and Ruthenium(II).- 2.3.3. Cobalt(-I), (II), and (III).- 2.3.4. Nickel(II) and Platinum(II).- 2.3.5. Copper(I) and (II).- 2.3.6. Stereoselective Electron Transfer.- 2.3.7. Excited State Reactions.- 2.3.8. Miscellaneous Reactions.- 2.4. Reactions with Metalloproteins.- 2.4.1. Introduction.- 2.4.2. Blue Copper Proteins.- 2.4.3. Hemoglobin and Myoglobin.- 2.4.4. Cytochromes.- 2.4.5. Iron-Sulfur Proteins.- 2.4.6. Hemerythrins.- 3. Metal-Ligand Redox Reactions.- 3.1. Introduction.- 3.2. Oxygen, Peroxide. Water. and Other Oxygen Compounds.- 3.2.1. Dioxygen.- 3.2.2. Hydrogen Peroxide.- 3.2.3. Alkyl Hydroperoxides, Peroxyl Acids. and Metal Peroxides.- 3.2.4. Water and Other Oxygen-Containing Compounds.- 3.3. Nitrogen Compounds and Oxyanions.- 3.3.1. Hydrazine, Azide. Hydroxylamine. and Derivatives.- 3.3.2. Nitrous Oxide, Nitrite. Nitrosonium, Trioxodinitrate Ions, and Nitric Acid.- 3.3.3. N-Oxide Compounds.- 3.3.4. Organic Amines.- 3.3.5. Bipyridinium Ions.- 3.3.6. Aryldiazonium Ions.- 3.4. Halogens. Halides, and Halogen Oxyacids.- 3.4.1. Halogens.- 3.4.2. Halides.- 3.4.3. Oxyhalides.- 3.4.4. Oscillating Reactions.- 3.5. Sulfur Compounds and Oxyanions.- 3.5.1. Peroxodisulfate.- 3.5.2. Sulfur Dioxide and Sulfite Ions.- 3.5.3. Dithionites.- 3.5.4. Thiosulfates.- 3.5.5. Sulfides, Thiols, and Disulfides.- 3.5.6. Sulfoxides.- 3.6. Phosphorus, Arsenic, and Oxycompounds.- 3.6.1. Phosphines/ Arsines.- 3.6.2. Phosphorus Oxyanions.- 3.6.3. Arsenious Compounds.- 3.7. Inorganic Radicals.- 3.8. Hydrogen.- 3.9. Ascorbic Acid, Quinols, Catechols, and Diols.- 3.9.1. Ascorbic Acid.- 3.9.2. Quinols and Catechols.- 3.9.3. Diols, Aliphatic and Aromatic Alcohols.- 3.10 Carboxylic Acids, Carboxylates, Carbon Dioxide, and Carbon Monoxide.- 3.10.1. Carboxylic Acids.- 3.10.2. Carbon Dioxide.- 3.10.3. Carbon Monoxide.- 3.1 1. Alkyl and Aryl Halides.- 3.12. Organic Radicals.- II. Substitutions 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 and Antimony.- 4.8. Oxygen.- 4.9. Sulfur.- 4.10. Selenium and Tellurium.- 4.11. Halogens and Xenon.- 4.11.1. Fluorine.- 4.11.2. Chlorine.- 4.11.3. Bromine.- 4.11.4. Iodine.- 4.11.5. Xenon.- 4.12. Oscillating Reactions.- 5. Substitution Reactions of Inert-Metal Complexes-Coordination Numbers 4 and 5.- 5.1. Introduction.- 5.2. Ligand Replacement at Square-Planar Platinum(II).- 5.3. Ligand Replacement at Square-Planar Palladium(II).- 5.4. Nickel(II) Complexes.- 5.5. Isomerization Reactions.- 5.6. Trans Effect.- 5.7. Five-Coordinate Compounds.- 5.8. Oxidative Additions.- 5.9. Rhodium(I) and Gold(III) Complexes.- 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+ Systems (L = OH2, NH3).- 6.2.2. Cr(III)—C Bond Rupture.- 6.2.3. Amine Complexes.- 6.2.4. Dechelation/Chelation Processes.- 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(V).- 6.9.3. Chromium(VI).- 6.10. Catalysis.- 6.1 1. 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. Cobaloximes and B12.- 7.9. Photochemistry.- 7.10. Miscellaneous.- 8. Substitution Reactions of Inert—Metal Complexes-Coordination Numbers 6 and Above: Other Inert Centers.- 8.1. Introduction.- 8.2. Molybdenum.- 8.3. Tungsten.- 8.4. Technetium.- 8.5. Rhenium.- 8.6. Iron.- 8.6.1. Pentacyanoferrates and Nitrosyls.- 8.6.2. Diimine Complexes.- 8.6.3. Other Complexes.- 8.7. Ruthenium.- 8.8. Osmium.- 8.9. Rhodium.- 8.10. Iridium.- 8.1 1. Platinum(1V).- 8.11.1. General.- 8.11.2. Intramolecular Processes.- 9. Substitution Reactions of Labile Metal Complexes.- 9.1. General.- 9.2. Complex Formation Involving Unsubstituted Metal Ions: Unidentate Ligand Substitution and Solvent Exchange.- 9.2.1. Bivalent Ions.- 9.2.2. Trivalent Ions.- 9.3. Complex Formation Involving Unsubstituted Metal Ions: Multidentate Ligand Substitution.- 9.3.1. Uni- and Bivalent Ions.- 9.3.2. Trivalent Ions.- 9.4. Complex Formation Involving Substituted Metal Ions: Ligand Substitution and Solvent Exchange.- 9.4.1. Uni- and Bivalent Ions.- 9.4.2. Trivalent Ions and Ions of Higher Valency.- 9.5. Ligand Substitution Processes in Dimeric Metal Complexes.- III. Reactions of Organometallic Compounds.- 10. Substitution and Insertion Reactions.- 10.1. Substitution Reactions.- 10.1.1. Mononuclear Complexes.- 10.1.2. Polynuclear Complexes.- 10.2. Insertion Reactions.- 10.2.1. Carbon Monoxide Insertion.- 10.2.2. Alkene Insertion.- 10.2.3. Miscellaneous Insertions.- 11. Metal-Alkyl and Metal-Hydride Bond Formation and Fission; Oxidative Addition and Reductive Elimination.- 11.1. Introduction.- 11.2. Dihydrogen and Trihydrogen 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. Oxidative Addition and Reductive Elimination of Alkyl Halides.- 11.6. Oxidative Addition and Reductive Elimination Involving Two Metal Centers.- 12. Reactivity of Coordinated Ligands.- 12.1. Introduction.- 12.2. Cobalt Complexes.- 12.2.1. Phosphate Esters.- 12.2.2. Carboxylic Acids, Esters, and Amides.- 12.3. Other Metal Complexes.- 12.3.1. Nucleophilic Addition to Nitriles.- 12.3.2. Nucleophilic Addition to Imines.- 12.3.3. Nucleophilic Addition to Carbonyls.- 12.3.4. Reactions of 1, 3-Dicarbonyls and Derivatives.- 12.3.5. Electrophilic Attack at Nitrogen and Oxygen.- 12.3.6. Reactions at Phosphorus.- 12.3.7. Reactions of Sulfur Ligands.- 12.3.8. Reactions of Heterocyclic Ligands.- 12.4. OrganometallicCompounds.- 12.4.1. Reactions with Nucleophiles.- 12.4.2. Reactions with Electrophiles.- 12.4.3. Reactions at Side Chains.- 13. Rearrangements. Intramolecular Exchanges. and Isomerizations 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. Rotation about the Metal-Metal Direction.- 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 Reactions.- 14. Homogeneous Catalysis of Organic Reactions by Transition Metal Complexes.- 14.1. General Reviews.- 14.2. Hydrogenations.- 14.2.1. Asymmetric Hydrogenations.- 14.3. Dehydrogenation and Hydrogen Transfer.- 14.4. Isomerizations.- 14.5. C—H Activation.- 14.6. Olefin Metathesis.- 14.7. Olefin Polymerizations.- 14.8. Alkyne Polymerizations.- 14.9. Hydrosilylations.- 14.10. Catalyzed Addition Reactions.- 14.11. Olefin Oligomerizations.- 14.12. Alkyne Oligomerizations.- 14.13. Carbonylations.- 14.13.1. Carbonylation of Alkenes and Alkynes.- 14.13.2. Hydroformylations.- 14.13.3. Water-Gas Shift Reactions.- 14.13.4. Ethylene Glycol Synthesis.- 14.13.5. Carbonylation of Alcohols and Amines.- 14.13.6. Carbonylation of Organic Halides.- 14.14. C—C 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.