Proton-Coupled Electron Transfer -- Contents -- CHAPTER 1 Application of the Marcus Cross Relation to Hydrogen Atom Transfer/Proton-Coupled Electron Transfer Reactions -- 1.1 Introduction -- 1.2 An Introduction to Marcus Theory -- 1.3 Predicting Organic Hydrogen Atom Transfer Rate Constants -- 1.3.1 Obtaining Self-Exchange Rate Constants and Equilibrium Constants -- 1.3.2 Tests of the Cross Relation for Organic HAT Reactions -- 1.3.3 Solvent Effects on HAT Rate and Equilibrium Constants -- 1.3.4 A Test Case: Reactions of Bulky Phenoxyl Radicals with TEMPOH -- 1.3.5 Tests of the Cross Relation using KSE-Corrected Self-Exchange Rate Constants -- 1.4 Predicting HAT Rate Constants for Transition Metal Complexes -- 1.4.1 Applying the Cross Relation as a Function of Temperature -- the Importance of Using Free Energies -- 1.4.2 Applying the Cross Relation to Oxidations by [RuIV (O)(bpy)2(py)]2+ -- 1.4.3 Precursor and Successor Complexes for HAT -- 1.4.4 Applying the Cross Relation for Transition Metal HAT -- 1.4.5 Transition Metal Systems that Deviate from the Cross Relation -- 1.5 Conclusions: Implications and Limitations of the Cross Relation for Hydrogen Atom Transfer Reactions -- References -- CHAPTER 2 A Transition-State Perspective of Proton-Coupled Electron Transfers -- 2.1 Introduction -- 2.2 Theory -- 2.2.1 Hydrogen Atom Transfers -- 2.2.2 Proton Transfers in Hydrogen-Bonded Systems -- 2.2.3 Electron Transfers -- 2.2.4 Concerted Proton-Electron Transfers -- 2.3 Applications -- 2.3.1 HAT in the Benzyl/Toluene Self-Exchange -- 2.3.2 PCET in the Phenoxyl/Phenol Self-Exchange -- 2.3.3 CPET in Soybean Lipoxygenase-1 -- 2.4 Conclusions -- References -- CHAPTER 3 Experimental Approaches Towards Proton-Coupled Electron Transfer Reactions in Biological Redox Systems -- 3.1 Introduction -- 3.1.1 Definitions -- 3.1.2 Thermodynamics of PCET Reactions.

3.1.3 Kinetics of PCET Reactions -- 3.2 Experimental Kinetic Approaches to Analyse PCET Reactions -- 3.3 Case Studies -- 3.3.1 PCET in Nitrite Reductase -- 3.3.2 Hydride Transfer Reactions in Old Yellow Enzymes -- 3.4 Concluding Remarks -- References -- CHAPTER 4 Metal Ion-Coupled and Proton-Coupled Electron Transfer in Catalytic Reduction of Dioxygen -- 4.1 Introduction -- 4.2 PCET from Electron Donors to O2 -- 4.3 MCET from Electron Donors to O2 -- 4.4 MCET from O2--Mn+ to p-Benzoquinones -- 4.5 Catalytic Two-Electron Reduction of O2 via MCET and PCET -- 4.6 Catalytic Four-Electron Reduction of O2 -- 4.6.1 Cofacial Dicobalt Porphyrin and Porphyrin-Corrole Dyads -- 4.6.2 Mononuclear Cu Complexes -- 4.6.3 A Heterodinuclear Iridium-Ruthenium Complex -- 4.6.4 Mononuclear Mn Complexes -- 4.7 Summary and Conclusions -- Acknowledgements -- References -- CHAPTER 5 Proton-Coupled Electron Transfer in Natural and Artificial Photosynthesis -- 5.1 Introduction -- 5.2 Proton-Coupled Electron Transfer Reactions -- 5.2.1 Interfacial PCET -- 5.3 Thermodynamics of Water Splitting and CO2 Reduction -- 5.4 Natural Photosynthesis -- 5.4.1 Structure and Mechanism of Photosystem II -- 5.4.2 PCET in Photosystem II -- 5.5 Artificial Photosynthesis -- 5.5.1 Model Systems for Photosystem II -- 5.5.2 Water Oxidation Catalysts -- 5.5.3 Proton and CO2 Reduction -- 5.6 Concluding Remarks -- References -- Subject Index.