Inorganic Reactions and Methods V15 – Electron– Transfer & Electrochemical Reactions, Photochemical & Other Energized Reactions

"Inorganic Reactions and Methods Volume 15" is edited by J. J. Zuckerman.

Table of 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