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The subject of the book is electron transfer reactions in organic chemistry, with the emphasis on mechanistic aspects. The theoretical framework is that of the Marcus theory, well-known from its extensive use in inorganic chemistry. The book deals with definitions of electron transfer, theory of electron transfer reactions (Marcus' and Pross-Shaik's approach) experimental diagnosis of electron transfer reactions, examples from inorganic/organic reactants and purely organic reactants, electro- and photochemical electron transfer, electron transfer catalyzed reactions, connections between electron transfer and polar mechanisms, and applications of electron transfer, such as electrosynthesis of organic chemicals, photochemical energy storage, conducting organic materials and chemiluminescence. The approach is new in so far as no comparable book has been published. The book will be of value to anyone interested in keeping track of developments in physical organic chemistry.
List of contents
I Electron Transfer, a Neglected Concept in Organic Chemistry.- I.1 Electron Transfer is Fundamental in Many Areas of Organic Chemistry.- I.2 Organic Electron Transfer Theories Come in Cycles.- I.3 References.- II Concepts and Definitions.- II.1 Electron Transfer Can Be Defined in Several Ways.- II.2 Inner-and Outer-sphere Electron Transfer.- II.3 Other Concepts in Electron Transfer Chemistry.- II.4 References.- III Theories of Electron Transfer in Organic Chemistry.- III.1 The Thermodynamic Approach to Electron Transfer Reactivity.- III.2 The Single Electron Shift, a Configuration Mixing Model of Electron Transfer Reactivity.- III.3 The Marcus Theory for Outer-sphere ET.- III. 4 Kinetic Models of Electron Transfer Mechanisms.- III.5 The Marcus Inverted Region.- III.6 The Rehm-Weiler and Agmon-Levine Equations.- III.7 References.- IV How to Use the Marcus Theory.- IV.1 Standard Potential.- IV.2 Reorganization Energy.- IV.3 Case Studies.- IV.4 References.- V Experimental Diagnosis.- V.l Phenomenological Approach.- V.2 Mechanistic Approach.- V.3 Summarizing Remarks.- V.4 References.- VI Reactions Between Organic and Inorganic Non-metallic Species.- V.1 Oxygen Derived Species.- VI.2 Sulfur Derived Species.- VI.3 Nitrogen Derived Species.- VI.4 Halogen Derived Species.- VI.5 Miscellaneous.- VI.6 Summarizing Remarks.- IV.7 References.- VII Reaction Between Organic and Metal Ion Species.- VII.1 One-and Two-electron Reagents.- VII.2 Choice of Metal Reagent and Substrate in Mechanistic Studies.- VII.3 Examples of Established Outer-sphere Mechanisms.- VII.4 Specific Systems.- VII.5 Conclusion.- VII.6 References.- VIII Electron Transfer Reactions Between Organic Species.- VIII. 1 Radical Ions and Radicals as ET Reagents.- VIII.2 Organic Ions and Even-electron Molecules as ET Reagents.- VIII.3 References.- IX Electricity and Light Promoted ET.- IX.1 Organic Electrode Processes.- IX.2 Photochemical ET.- IX. 3 Photoelectrochemistry.- IX.4 Chemiluminescence.- IX.5 References.- X Electron Transfer Catalyzed Reactions.- X.1 Electron Transfer Catalysis as a General Phenomenon.- X.2 An Overview of the ETC Process.- X.3 Different Types of ETC Reactions.- X.4 References.- XI ET and Polar Mechanisms; How Are They Connected?.- XI.1 Formulation of the Problem.- XI. 2 Electrophilic Aromatic Substitution.- XI.3 The SN2 Mechanism.- XI.4 Conclusions.- IX.5 References.- XII Applications of Outer-sphere Electron Transfer.- XII.1 Introduction.- XII.2 Photochemical Fuel Production.- XII.3 Light from Chemical Reactions (Chemiluminescence).- XII.4 Synthetic Applications of ET Reactions.- XII. 5 Conducting Organic Materials.- XII.6 Molecular Electronic Devices of Organic Origin.- XII.7 Oscillating Reactions.- XII.8 Wood Pulping and ET.- XII.9 Toxicity and ET.- XII.10 Degradation Mechanisms of Organic Compounds.- XII.11 References.- Epilogue.
