Cover -- Title Page -- Copyright -- Contents -- List of Contributors -- Preface -- Chapter 1 Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis -- 1.1 Introduction -- 1.2 Structural Studies of the OEC -- 1.3 The Dark-Stable State of the OEC -- 1.4 Biomimetic Oxomanganese Complexes -- 1.5 Base-Assisted O-O Bond Formation -- 1.6 Biomimetic Mn Catalysts for Artificial Photosynthesis -- 1.7 Conclusion -- Acknowledgments -- References -- Chapter 2 O-O Bond Formation by a Heme Protein: The Unexpected Efficiency of Chlorite Dismutase -- 2.1 Introduction -- 2.2 Origins of O2-Evolving Chlorite Dismutases (Clds) -- 2.3 Major Structural Features of the Proteins and their Active Sites -- 2.4 Efficiency, Specificity, and Stability -- 2.5 Mechanistic Insights from Surrogate Reactions with Peracids and Peroxide -- 2.6 Possible Mechanisms -- 2.7 Conclusion -- Acknowledgements -- References -- Chapter 3 Ru-Based Water Oxidation Catalysts -- 3.1 Introduction -- 3.2 Proton-Coupled Electron Transfer (PCET) and Water Oxidation Thermodynamics -- 3.3 O-O Bond Formation Mechanisms -- 3.4 Polynuclear Ru Water Oxidation Catalysts -- 3.5 Mononuclear Ru WOCs -- 3.6 Anchored Molecular Ru WOCs -- 3.7 Light-Induced Ru WOCs -- 3.8 Conclusion -- Acknowledgments -- References -- Chapter 4 Towards the Visible Light-Driven Water Splitting Device: Ruthenium Water Oxidation Catalysts with Carboxylate-Containing Ligands -- 4.1 Introduction -- 4.2 Binuclear Ru Complexes -- 4.3 Mononuclear Ru Complexes -- 4.3.1 Ru-O2N-N3 Analogs -- 4.3.2 Ru-O2N2-N2 Analogs -- 4.4 Homogeneous Light-Driven Water Oxidation -- 4.4.1 The Three-Component System -- 4.4.2 The Supramolecular Assembly Approach -- 4.5 Water Oxidation Device -- 4.5.1 Electrochemical Water Oxidation Anode -- 4.5.2 Photo-Anode for Water Oxidation -- 4.6 Conclusion -- References.

Chapter 5 Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands -- 5.1 Introduction -- 5.2 Water Oxidation Catalyzed by Dinuclear Ruthenium Complexes with NILs -- 5.3 Water Oxidation by Intramolecular O-O Coupling with [Ru II2(μ-Cl)(bpy)2(btpyan)]3+ -- 5.4 Mononuclear Ru-Aqua Complexes with a Dioxolene Ligand -- 5.4.1 Structural Characterization -- 5.4.2 Theoretical and Electrochemical Characterization -- 5.5 Mechanistic Investigation of Water Oxidation by Dinuclear Ru Complexes with NILs: Characterization of Key Intermediates -- References -- Chapter 6 Recent Advances in the Field of Iridium-Catalyzed Molecular Water Oxidation -- 6.1 Introduction -- 6.2 Bernhard 2008 [11] -- 6.3 Crabtree 2009 [12] -- 6.4 Crabtree 2010 [13] -- 6.5 Macchioni 2010 [14] -- 6.6 Albrecht/Bernhard 2010 [15] -- 6.7 Hetterscheid/Reek 2011 [16,17] -- 6.8 Crabtree 2011 [18] -- 6.9 Crabtree 2011 [19] -- 6.10 Lin 2011 [20] -- 6.11 Macchioni 2011 [21] -- 6.12 Grotjahn 2011 [22] -- 6.13 Fukuzumi 2011 [23] -- 6.14 Lin 2012 [24] -- 6.15 Crabtree 2012 [25-27] -- 6.16 Albrecht/Bernhard 2012 [28] -- 6.17 Crabtree 2012 [29] -- 6.18 Beller 2012 [30] -- 6.19 Lin 2012 [31] -- 6.20 Lloblet and Macchioni 2012 [33] -- 6.21 Analysis -- References -- Chapter 7 Complexes of First Row d-Block Metals: Manganese -- 7.1 Background -- 7.2 Oxidation States of Manganese in an Aqueous Environment -- 7.3 Dinuclear Manganese Complexes: Syntheses and Structures -- 7.4 Redox and Acid-Base Chemistry of Mn2- -WDL Systems -- 7.5 Mn2 Systems: Oxygen Evolution (but not Water Oxidation) Catalysis -- 7.6 Mn2 Complexes/the OEC/Ru2 Catalysts: A Comparison -- 7.7 Heterogeneous Water Oxidation Catalysis by Mn>2 Systems -- 7.8 Conclusion -- Acknowledgements -- References -- Chapter 8 Molecular Water Oxidation Catalysts from Iron -- 8.1 Introduction.

8.2 Fe-Tetrasulfophthalocyanine -- 8.3 Fe-TAML -- 8.4 Fe-mcp -- 8.5 Fe2O3 as a Microheterogeneous Catalyst -- 8.6 Conclusion -- References -- Chapter 9 Water Oxidation by Co-Based Oxides with Molecular Properties -- 9.1 Introduction -- 9.2 CoCat Formation -- 9.3 Structure and Structure-Function Relations -- 9.4 Functional Characterization -- 9.5 Directly Light-Driven Water Oxidation -- References -- Chapter 10 Developing Molecular Copper Complexes for Water Oxidation -- 10.1 Introduction -- 10.2 A Biomimetic Approach -- 10.2.1 Thermochemistry: Developing Oxidant/Base Combinations as PCET Reagents -- 10.2.2 Copper Complexes with Alkylamine Ligands -- 10.2.3 Copper Complexes with Anionic Ligands -- 10.2.4 Lessons Learned: Thermochemical Insights and Oxidant/Base Compatibility -- 10.3 An Aqueous System: Electrocatalysis with (bpy)Cu(II) Complexes -- 10.3.1 System Selection: bpy + Cu -- 10.3.2 Observing Electrocatalysis -- 10.3.3 Catalyst Turnover Number and Turnover Frequency -- 10.3.4 Catalyst Speciation: Monomer, Dimer, or Nanoparticles? -- 10.4 Conclusion -- Acknowledgement -- References -- Chapter 11 Polyoxometalate Water Oxidation Catalytic Systems -- 11.1 Introduction -- 11.2 Recent POM WOCs -- 11.3 Assessing POM WOC Reactivity -- 11.4 The Ru(oxbpy)32+/S2O82- System -- 11.5 Ru(bpy)33+ as an Oxidant for POM WOCs -- 11.6 Additional Aspects of WOC System Stability -- 11.7 Techniques for Assessing POM WOC Stability -- 11.8 Conclusion -- Acknowledgments -- References -- Chapter 12 Quantum Chemical Characterization of Water Oxidation Catalysts -- 12.1 Introduction -- 12.2 Computational Details -- 12.2.1 Density Functional Theory Calculations -- 12.2.2 Multiconfigurational Calculations -- 12.3 Methodology -- 12.3.1 Solvation and Standard Reduction Potentials -- 12.3.2 Multideterminantal State Energies.

12.4 Water Oxidation Catalysts -- 12.4.1 Ruthenium-Based Catalysts -- 12.4.2 Cobalt-Based Catalysts -- 12.4.3 Iron-Based Catalysts -- 12.5 Conclusion -- References -- Index -- Supplemental Images.