Mechanisms of Inorganic and Organometallic Reactions Volume 7

ISBN-13: 9781461366508 / Angielski / Miękka / 2012 / 463 str.

M. V. Twigg

Opis

The current volume covers electron transfer reactions, substitution and relation reactions, and reactions of organometallic compounds.

Spis treści

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.