Proton-coupled electron transfer : a carrefour of chemical reactivity traditions / editors, Sebastião Formosinho and Mónica Barroso.

Format:

Book

Contributor:

Formosinho, Sebastião J., 1943-

Barroso, Mónica.

Series:

RSC catalysis series

Language:

English

Subjects (All):

Charge exchange.

Electron donor-acceptor complexes.

Proton transfer reactions.

Physical Description:

ix, 157 pages : illustrations ; 24 cm.

Place of Publication:

Cambridge : Royal Society of Chemistry, [2012]

Summary:

This book covers the most recent developments in the field of PCET reactions, from the theoretical and experimental points of view. 200 pp.

Contents:

Chapter 1 Application of the Marcus Cross Relation to Hydrogen Atom Transfer/Proton-Coupled Electron Transfer Reactions / Jeffrey J. Warren Warren, Jeffrey J., James M. Mayer Mayer, James M. 1

1.1 Introduction 1

1.2 An Introduction to Marcus Theory 2

1.3 Predicting Organic Hydrogen Atom Transfer Rate Constants 5

1.3.1 Obtaining Self-Exchange Rate Constants and Equilibrium Constants 6

1.3.2 Tests of the Cross Relation for Organic HAT Reactions 7

1.3.3 Solvent Effects on HAT Rate and Equilibrium Constants 11

1.3.4 A Test Case: Reactions of Bulky Phenoxyl Radicals with TEMPOH 12

1.3.5 Tests of the Cross Relation using KSE-Corrected Self-Exchange Rate Constants 13

1.4 Predicting HAT Rate Constants for Transition Metal Complexes 14

1.4.1 Applying the Cross Relation as a Function of Temperature; the Importance of Using Free Energies 16

1.4.2 Applying the Cross Relation to Oxidations by [Ru^IV(O)(bpy)₂(py)]²⁺ 17

1.4.3 Precursor and Successor Complexes for HAT 18

1.4.4 Applying the Cross Relation for Transition Metal HAT 20

1.4.5 Transition Metal Systems that Deviate from the Cross Relation 21

1.5 Conclusions: Implications and Limitations of the Cross Relation for Hydrogen Atom Transfer Reactions 23

References 27

Chapter 2 A Transition-State Perspective of Proton-Coupled Electron Transfers / Luis G. Arnaut Arnaut, Luis G. 32

2.1 Introduction 32

2.2 Theory 34

2.2.1 Hydrogen Atom Transfers 34

2.2.2 Proton Transfers in Hydrogen-Bonded Systems 37

2.2.3 Electron Transfers 40

2.2.4 Concerted Proton-Electron Transfers 47

2.3 Applications 48

2.3.1 HAT in the Benzyl/Toluene Self-Exchange 48

2.3.2 PCET in the Phenoxyl/Phenol Self-Exchange 50

2.3.3 CPET in Soybean Lipoxygenase-1 52

2.4 Conclusions 53

References 54

Chapter 3 Experimental Approaches Towards Proton-Coupled Electron Transfer Reactions in Biological Redox Systems / Sibylle Brenner Brenner, Sibylle, Sam Hay Hay, Sam, Derren J. Heyes Heyes, Derren J., Nigel S. Scrutton Scrutton, Nigel S. 57

3.1 Introduction 57

3.1.1 Definitions 57

3.1.2 Thermodynamics of PCET Reactions 61

3.1.3 Kinetics of PCET Reactions 64

3.2 Experimental Kinetic Approaches to Analyse PCET Reactions 69

3.3 Case Studies 73

3.3.1 PCET in Nitrite Reductase 73

3.3.2 Hydride Transfer Reactions in Old Yellow Enzymes 76

3.4 Concluding Remarks 79

References 79

Chapter 4 Metal Ion-Coupled and Proton-Coupled Electron Transfer in Catalytic Reduction of Dioxygen / Shunichi Fukuzumi Fukuzumi, Shunichi, Hiroaki Kotani Kotani, Hiroaki 89

4.1 Introduction 89

4.2 PCET from Electron Donors to O₂ 91

4.3 MCET from Electron Donors to O₂ 97

4.4 MCET from O₂·-Mⁿ⁺ to p-Benzoquinones 99

4.5 Catalytic Two-Electron Reduction of O₂ via MCET and PCET 103

4.6 Catalytic Four-Electron Reduction of O₂ 109

4.6.1 Cofacial Dicobalt Porphyrin and Porphyrin-Corrole Dyads 109

4.6.2 Mononuclear Cu Complexes 115

4.6.3 A Heterodinuclear Indium-Ruthenium Complex 118

4.6.4 Mononuclear Mn Complexes 119

4.7 Summary and Conclusions 121

Acknowledgements 121

References 121

Chapter 5 Proton-Coupled Electron Transfer in Natural and Artificial Photosynthesis / M. Barroso Barroso, M., Luis G. Amaut Amaut, Luis G., Sebastiao J. Formosinho Formosinho, Sebastiao J. 126

5.1 Introduction 126

5.2 Proton-Coupled Electron Transfer Reactions 128

5.2.1 Interfacial PCET 129

5.3 Thermodynamics of Water Splitting and CO₂ Reduction 130

5.4 Natural Photosynthesis 132

5.4.1 Structure and Mechanism of Photosystem II 133

5.4.2 PCET in Photosystem II 136

5.5 Artificial Photosynthesis 137

5.5.1 Model Systems for Photosystem II 138

5.5.2 Water Oxidation Catalysts 139

5.5.3 Proton and CO2 Reduction 144

5.6 Concluding Remarks 145.

Notes:

Includes bibliographical references and index.

ISBN:

9781849731416

1849731411

OCLC:

775022821