Inorganic Reactions and Methods: v. 15 Electron-transfer and Electrochemical Reactions; Photochemical and Other Energized Reactions (Inorganic Reactio

Inorganic Reactions and Methods: v. 15 Electron-transfer and Electrochemical Reactions; Photochemical and Other Energized Reactions (Inorganic Reactio

By: J. J. Zuckerman (author)Hardback

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Inorganic Reactions and Methods Volume 15 Editor J. J. Zuckerman

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Contents

How to Use this Book; Preface to the Series; Editorial Consultants to the Series; Contributors to Volume 15; 12. Electron--Transfer and Electrochemical Reactions; 12.1. Introduction; 12.2. Electron Transfer; 12.2.1. Introduction; 12.2.2. Classification of Electron--Transfer Reactions; 12.2.2.1. Outer--Sphere Reactions; 12.2.2.1.1. Examples of Outer--Sphere Reactions; 12.2.2.1.2. Outer--Sphere Transition States; 12.2.2.2. Inner--Sphere Reactions; 12.2.2.2.1. Inner--Sphere Reactions: Scheme I; 12.2.2.2.2. Inner--Sphere Reactions: Scheme II; 12.2.2.2.3. Inner--Sphere Reactions: Scheme III; 12.2.2.2.4. Double--Ligand Bridging; 12.2.2.3. Other Reaction Classes; 12.2.2.3.1. Mixed Outer-- and Inner--Sphere Reactions; 12.2.2.3.2. Intramolecular Electron Transfer; 12.2.2.3.3. Two--Electron Transfers; 12.2.3. Theory of Electron--Transfer Reactions; 12.2.3.1. The Stability of the Precursor Complex; 12.2.3.2. Potential--Energy Surfaces; 12.2.3.2.1. of Zero Order.; 12.2.3.2.2. of First Order.; 12.2.3.2.3. The Electronic Factor; 12.2.3.3. Electron--Exchange Reactions; 12.2.3.3.1. The Reorganization Energy; 12.2.3.3.2. Nuclear Tunneling in Electron Exchange; 12.2.3.3.3. Quantum--Mechanical Treatment; 12.2.3.3.4. Comparison of Observed and Calculated; Parameters for Electron Exchange; Electron Transfer; Theory of Electron--Transfer Reactions; 12.2.3.4. Electron Transfer Accompanied by a Net Chemical Change; 12.2.3.4.1. Semiclassical Treatment; 12.2.3.4.2. Cross Reactions and Electron--Exchange Rates; 12.2.3.4.3. Quantum--Mechanical Treatment; 12.2.3.5. Conclusions; 12.2.4. General Reactivity Patterns in Electron Transfer; 12.2.4.1. The Inner--Shell Reorganization Energy: Exchange Rates of Aquo Ions; 12.2.4.2. Variations with Ligand: The Outer--Shell Reorganization Energy; 12.2.4.3. Electronic Factors: Nonadiabaticity; 12.2.4.4. Free--Energy Relations; 12.2.4.5. Inner--Sphere Versus Outer--Sphere Electron Transfer; 12.2.4.6. Rate Saturation in Electron Transfer; 12.2.5. Specific Reactivity Patterns in Electron--Transfer Reactions; 12.2.5.1. Variation with the Reductant; 12.2.5.1.1. One--Electron Reductants; 12.2.5.1.2. Two--Electron Reductants; 12.2.5.2. Variation with the Oxidant; 12.2.5.2.1. One--Electron Oxidants; 12.2.5.2.2. Multiple--Electron Oxidants; 12.2.5.3. Oxidation and Reduction of Coordinated Ligands; 12.2.5.4. Catalysis in Electron--Transfer Reactions; 12.2.5.4.1. Catalyzed Electron Transfer; 12.2.5.4.2. Catalyzed Ligand Substitution; 12.2.5.5. Induced Electron--Transfer Reactions; 12.2.5.6. Photoinduced Electron--Transfer Reactions; 12.3. Electrochemical Reactions; 12.3.1. Introduction; 12.3.1.1. The Electrode Process; 12.3.1.2. Reversibility; 12.3.1.2.1. Electrochemical Reversibility; 12.3.1.2.2. Chemical Reversibility; 12.3.1.3. Complex Electrode Mechanisms; 12.3.2. Diagnostic Electrochemical Measurements; 12.3.2.1. Voltammetric Methods; 12.3.2.1.1. Direct--Current Polarography; 12.3.2.1.2. Pulse--Polarographic Methods; 12.3.2.1.3. Alternating--Current Polarography; 12.3.2.1.4. Cyclic Voltammetry; 12.3.3. Evaluation of Formal Potentials; 12.3.3.1. Involving Stable Reactants and Products.; 12.3.3.2. Involving Unstable Electrode Products.; 12.3.3.3. Involving Reactants Undergoing Multiple--Electrode Reactions.; 12.3.4. Chemical Reactions Accompanying Electrode Reactions; 12.3.4.1. Reactions Preceding Electron Transfer (CE); 12.3.4.1.1. Slow--Reaction (1 a) Limit; 12.3.4.1.2. Fast--Reaction (1 a) Limit; 12.3.4.1.3. Intermediate--Reaction Kinetics; 12.3.4.2. Reactions Following Electron Transfer (EC); 12.3.4.2.1. Giving Electroinactive Products.; 12.3.4.2.2. Giving Electroactive Products (ECE).; 12.3.4.3. Other Coupled Chemical Reactions; 12.3.5. Electrochemical Synthesis; 12.3.5.1. by Controlled--Potential Electrolysis.; 12.3.5.2. Involving Bulk Preparations.; 12.3.5.3. Conclusions; 12.3.6. Thermodynamics of Simple Electrochemical Reactions; 12.3.7. Kinetics of Electrochemical Reactions; 12.3.7.1. Basic Characteristics; 12.3.7.2. Theory of Heterogeneous Electron--Transfer Reactions; 12.3.7.3. Double--Layer Effects in Electrochemical Kinetics; 12.3.7.4. Electrode--Reaction Mechanisms; 12.3.7.5. Influence of the Electrode Material; 12.3.7.6. Electrochemical Reactivity Patterns - Comparisons with Homogeneous Reactivities; 13. Photochemical and Other Energized Reactions; 13.1. Introduction; 13.2. Photosubstitution and Photoisomerization; 13.2.1. with Group VIA Complexes; 13.2.1.1. of Chromium(III).; 13.2.1.2. of Molybdenum and Tungsten.; Photosubstitution and Photoisomerization; 13.2.2. with Group VIIA Complexes.; 13.2.3. with Group VIII Complexes; 13.2.3.1. of Iron.; 13.2.3.2. of Ruthenium.; 13.2.3.3. of Osmium.; 13.2.3.4. of Cobalt.; 13.2.3.5. of Rhodium(III) and Iridium(III).; 13.2.3.6. of Nickel(II) and Palladium(II).; 13.2.3.7. of Platinum(II).; 13.2.3.8. of Platinum(IV).; 13.2.4. with Metal Carbonyls; 13.2.4.1. involving Mononuclear Complexes; 13.2.4.1.1. of Titanium, Zirconium and Hafnium.; 13.2.4.1.2. of Vanadium, Niobium and Tantalum.; 13.2.4.1.3. of Chromium, Molybdenum and Tungsten.; 13.2.4.1.4. of Manganese and Rhenium.; 13.2.4.1.5. of Iron, Ruthenium and Osmium.; 13.2.4.1.6. of Cobalt, Rhodium and Iridium.; 13.2.4.1.7. of Nickel.; 13.2.4.2. Involving Dinuclear Complexes.; 13.2.4.3. Involving Polynuclear Complexes.; 13.2.5. with Other Organometallic Complexes; 13.2.5.1. Containing Metal Hydrides.; 13.2.5.2. Containing isocyanides.; 13.2.5.3. Containing Olefins.; 13.2.5.4. Containing Arenes and Cyclopentadienyls.; 13.2.5.5. Containing Alkyls.; 13.3. Photoinduced Cleavage of Metal - Metal Bonds; 13.3.1. in Dinuclear Complexes; 13.3.1.1. That Are Homonuclear; 13.3.1.1.1. and Contain Chromium, Molybdenum and Tungsten.; 13.3.1.1.2. and Contain Manganese, Technetium and Rhenium.; 13.3.1.1.3. and Contain Iron and Ruthenium.; 13.3.1.1.4. and Contain Cobalt.; 13.3.1.1.5. and Contain Nickel, Palladium and Platinum.; 13.3.1.2. That Are Heteronuclear.; 13.3.2. in Polynuclear Complexes.; 13.4. Photoinduced Electron--Transfer Reactions; 13.4.1. Excited--State Assignments; 13.4.2. Excited--State Electron Exchange; 13.4.3. Quenching and Back Reactions; 13.4.4. Free--Energy Relations; 13.5. Pulse Radiolysis; 13.5.1. Introduction; 13.5.2. Principles; 13.5.3. Techniques; 13.5.4. by Radiation Generation; 13.5.4.1. of Hydrated Electrons.; 13.5.4.2. of Hydroxyl Radicals.; 13.5.4.3. of Hydrogen Atoms.; 13.5.4.4. of Secondary Radicals.; 13.5.5. of Metal Complexes; 13.5.5.1. Involving Groups IA and IIA.; 13.5.5.2. Involving Group IIIA.; 13.5.5.3. Involving Group IVA.; 13.5.5.4. Involving Group VA.; 13.5.5.5. Involving Group VIA; 13.5.5.5.1. with Chromium.; 13.5.5.5.2. with Molybdenum and Tungsten.; 13.5.5.6. Involving Group VIIA; 13.5.5.6.1. with Manganese.; 13.5.5.6.2. with Technetium.; 13.5.5.7. Involving Group VIIIA; 13.5.5.7.1. with Iron.; 13.5.5.7.2. with Ruthenium.; 13.5.5.7.3. with Osmium.; 13.5.5.7.4. with Cobalt.; 13.5.5.7.5. with Rhodium.; 13.5.5.7.6. with Iridium.; 13.5.5.7.7. with Nickel.; 13.5.5.7.8. with Palladium and Platinum.; 13.5.5.8. Involving Group lB; 13.5.5.8.1. with Copper.; 13.5.5.8.2. with Silver.; 13.5.5.8.3. with Gold.; 13.5.5.9. Involving Group lib; 13.5.5.9.1. with Zinc.; 13.5.5.9.2. with Cadmium.; 13.5.5.9.3. with Mercury.; Pulse Radiolysis; of Metal Complexes; 13.5.5.10. Involving Group IIIB; 13.5.5.10.1. with Gallium.; 13.5.5.10.2. with Indium.; 13.5.5.10.3. with Thallium.; 13.5.5.11. Involving Group IVB; 13.5.5.11.1. with Tin.; 13.5.5.11.2. with Lead.; 13.5.5.12. Involving Lanthanides.; 13.5.5.13. Involving Actinides.; List of Abbreviations; Author Index; Compound Index; Subject Index

Product Details

  • publication date: 07/11/1986
  • ISBN13: 9780471186656
  • Format: Hardback
  • Number Of Pages: 424
  • ID: 9780471186656
  • weight: 762
  • ISBN10: 0471186651

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