Mechanisms of Inorganic and Organometallic Reactions: Volume 3

ISBN-13: 9781461295037 / Angielski / Miękka / 2012 / 519 str.

M. V. Twigg

Opis

The purpose of this series is to provide a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organo metallic reactions in solution, with coverage being complete in each volume. The papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms and many include results of a nonkinetic nature when useful mechanistic information can be deduced. The period of literature covered by this volume is July 1982 through December 1983, and in some instances papers not available for inclusion in the previous volume are also included. Numerical results are usually reported in the units used by the original authors, except where data from different papers are com pared and conversion to common units is necessary. As in previous volumes material included covers the major areas of redox processes, reactions of the nonmetallic elements, reaction of inert and labile metal complexes and the reactions of organometallic compounds. While maintaining the space devoted to other areas, that given to the nonmetallic elements has been increased. In recognition of the increasing importance of the determination of volumes of activation in understanding the mechanisms of both inorganic and organometallic reactions a special reference section giving tabulated Ll V* values has been included and this extensive compilation will be updated in future volumes."

Spis treści

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.