Electron Transfer Reactions in Organic Chemistry

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.3.a The Physical Model.- 111.3. b The Marcus Equation.- III.3.c Properties of the Marcus Expression.- III. 4 Kinetic Models of Electron Transfer Mechanisms.- III.4.a The Collide-and React Model.- III.4.b The Kinetic Model of Reversible Electron Transfer.- 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.3.a Oxidation of Alkylmetals by Fe(III) Complexes.- IV.3.b Oxidation of NADH by Ferrieinium Ions.- IV.3.c Reduction of N-bromosuccinimide by Ferrocenes and Other Easily Oxidizable Compounds.- IV.4 References.- V Experimental Diagnosis.- V.l Phenomenological Approach.- V.2 Mechanistic Approach.- V 2.a Detection of Radicals by ESR Spectroscopy.- V.2.b Trapping of Radical Intermediates.- V.2.c Stereochemistry.- V.2.d Formation of Radical-derived Products.- V.2.e Kinetic Methods.- V.2.f Isotope Effects.- V.2.g Failures of Simple LFERs.- V.2.h Comparison with Compulsory ET Reactions.- V.2.i Photostimulation.- V.2.j Appearance of Charge-transfer Complexes.- V.2.k Chemiluminescence.- 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.4.a Co(III) Oxidation.- VII.4.b Mn(III) Oxidation.- VII.4.c Ag(II) Oxidation.- VII.4.d Cu(III) Oxidation.- VII.4.e Cu(II) Oxidation.- VII.4.f Ce(IV) Oxidation.- VII.4.g Ir(IV) Oxidation.- VII.4.h Ni(IV) and Ni(III) Oxidation.- VII.4.i Tl(III) Oxidation.- VII.4.j Pb(IV) Oxidation.- VII.4.k Pd(II) Oxidation.- VII.5 Conclusion.- VII.6 References.- VIII Electron Transfer Reactions Between Organic Species.- VIII. 1 Radical Ions and Radicals as ET Reagents.- VIII.1.a Reduction of Halides by Radical Anions.- VIII.l.b Reduction of Halides by Metal Reagents.- VIII.1.c Reduction of Polyhalides by ET Reagents.- VIII.l.d Reaction Between Radical Cations and Carboxylate Ions.- VIII.l.e ET Reactions Between Radicals and Neutral Organic Species.- VIII.2 Organic Ions and Even-electron Molecules as ET Reagents.- VIII.2.a Carbanions as ET Reductants.- VIII.2.b Alkyllithiums and Grignard Reagents as ET Reagents.- VIII.2.c Other Main Group Organometallics as ET Reagents.- VIII.2.d NADH as a Potential ET Reagent.- VIII.2.e Peroxide Derivatives as ET Oxidants.- VIII.3 References.- IX Electricity and Light Promoted ET.- IX.1 Organic Electrode Processes.- IX.1.a An Overview of the Electrochemical Process.- IX.l.b The Nature of the Electrode/Electrolyte Interface.- IX.l.c The Activation Process of an Outer-Sphere Electrochemical Step.- IX.l.d Outer-sphere ET, the Sledgehammer Approach to Redox Chemistry.- IX.l.e Electrocatalysis.- IX.2 Photochemical ET.- IX.2.a A Simple MO Picture of Photochemical ET.- IX.2.b Application of the Marcus and Rehm-Weller Treatments to Photochemical ET.- IX.2.c Chemical Consequence

Product details

• Authors: Lennart Eberson
• Publisher: Springer, Berlin
• Languages: English
• Product format: Hardback
• Released: 01.01.1987
• EAN: 9783540175995
• ISBN: 978-3-540-17599-5
• No. of pages: 234
• Weight: 548 g
• Illustrations: XIII, 234 pp. 65 figs.
• Series: Reactivity and Structure: Concepts in Organic Chemistry; Reactivity and Structure: Concepts in Organic Chemistry
• Subject: Natural sciences, medicine, IT, technology > Chemistry > Organic chemistry