List of Contributors xi
Preface xv
1. Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis 1
Ivan Rivalta, Gary W. Brudvig, and Victor S. Batista
1.1 Introduction 1
1.2 Structural Studies of the OEC 2
1.3 The Dark-Stable State of the OEC 4
1.4 Biomimetic Oxomanganese Complexes 6
1.5 Base-Assisted O-O Bond Formation 7
1.6 Biomimetic Mn Catalysts for Artificial Photosynthesis 8
1.7 Conclusion 11
Acknowledgments 12
References 12
2. O-O Bond Formation by a Heme Protein: The Unexpected Efficiency of Chlorite Dismutase 15
Jennifer L. DuBois
2.1 Introduction 15
2.2 Origins of O2-Evolving Chlorite Dismutases (Clds) 15
2.3 Major Structural Features of the Proteins and their Active Sites 16
2.4 Efficiency, Specificity, and Stability 20
2.5 Mechanistic Insights from Surrogate Reactions with Peracids and Peroxide 22
2.6 Possible Mechanisms 23
2.7 Conclusion 25
Acknowledgements 25
References 25
3. Ru-Based Water Oxidation Catalysts 29
Laia Francas, Roger Bofill, Jordi Garcia-Anton, Lluis Escriche, Xavier Sala and Antoni Llobet
3.1 Introduction 29
3.2 Proton-Coupled Electron Transfer (PCET) and Water Oxidation Thermodynamics 31
3.3 O-O Bond Formation Mechanisms 33
3.4 Polynuclear Ru Water Oxidation Catalysts 34
3.5 Mononuclear Ru WOCs 40
3.6 Anchored Molecular Ru WOCs 42
3.7 Light-Induced Ru WOCs 43
3.8 Conclusion 45
Acknowledgments 46
References 46
4. Towards the Visible Light-Driven Water Splitting Device: Ruthenium Water Oxidation Catalysts with Carboxylate-Containing Ligands 51
Lele Duan, Lianpeng Tong, and Licheng Sun
4.1 Introduction 51
4.2 Binuclear Ru Complexes 52
4.3 Mononuclear Ru Complexes 54
4.3.1 Ru-O2N-N3 Analogs 55
4.3.2 Ru-O2N2-N2 Analogs 57
4.4 Homogeneous Light-Driven Water Oxidation 68
4.4.1 The Three-Component System 68
4.4.2 The Supramolecular Assembly Approach 69
4.5 Water Oxidation Device 72
4.5.1 Electrochemical Water Oxidation Anode 72
4.5.2 Photo-Anode for Water Oxidation 74
4.6 Conclusion 75
References 75
5. Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands 77
Tohru Wada, Koji Tanaka, James T. Muckerman, and Etsuko Fujita
5.1 Introduction 77
5.2 Water Oxidation Catalyzed by Dinuclear Ruthenium Complexes with NILs 81
5.3 Water Oxidation by Intramolecular O-O Coupling with [RuII2 (??-Cl)(bpy)2(btpyan)]3+ 85
5.4 Mononuclear Ru-Aqua Complexes with a Dioxolene Ligand 91
5.4.1 Structural Characterization 91
5.4.2 Theoretical and Electrochemical Characterization 96
5.5 Mechanistic Investigation of Water Oxidation by Dinuclear Ru Complexes with NILs: Characterization of Key Intermediates 101
References 107
6. Recent Advances in the Field of Iridium-Catalyzed Molecular Water Oxidation 113
James A. Woods, Stefan Bernhard, and Martin Albrecht
6.1 Introduction 113
6.2 Bernhard 2008 [11] 114
6.3 Crabtree 2009 115
6.4 Crabtree 2010 116
6.5 Macchioni 2010 117
6.6 Albrecht/Bernhard 2010 117
6.7 Hetterscheid/Reek 2011 118
6.8 Crabtree 2011 119
6.9 Crabtree 2011 120
6.10 Lin 2011 120
6.11 Macchioni 2011 122
6.12 Grotjahn 2011 123
6.13 Fukuzumi 2011 123
6.14 Lin 2012 124
6.15 Crabtree 2012 125
6.16 Albrecht/Bernhard 2012 125
6.17 Crabtree 2012 126
6.18 Beller 2012 127
6.19 Lin 2012 128
6.20 Lloblet and Macchioni 2012 129
6.21 Analysis 130
References 131
7. Complexes of First Row d-Block Metals: Manganese 135
Philipp Kurz
7.1 Background 135
7.2 Oxidation States of Manganese in an Aqueous Environment 137
7.3 Dinuclear Manganese Complexes: Syntheses and Structures 138
7.4 Redox and Acid-Base Chemistry of Mn2-??-WDL Systems 139
7.5 Mn2 Systems: Oxygen Evolution (but not Water Oxidation) Catalysis 142
7.6 Mn2 Complexes/the OEC/Ru2 Catalysts: A Comparison 144
7.7 Heterogeneous Water Oxidation Catalysis by Mn>2 Systems 146
7.8 Conclusion 148
Acknowledgements 148
References 149
8. Molecular Water Oxidation Catalysts from Iron 153
W. Chadwick Ellis, Neal D. McDaniel, and Stefan Bernhard
8.1 Introduction 153
8.2 Fe-Tetrasulfophthalocyanine 154
8.3 Fe-TAML 155
8.4 Fe-mcp 157
8.5 Fe2O3 as a Microheterogeneous Catalyst 158
8.6 Conclusion 160
References 161
9. Water Oxidation by Co-Based Oxides with Molecular Properties 163
Marcel Risch, Katharina Klingan, Ivelina Zaharieva, and Holger Dau
9.1 Introduction 163
9.2 CoCat Formation 164
9.3 Structure and Structure-Function Relations 166
9.4 Functional Characterization 173
9.5 Directly Light-Driven Water Oxidation 175
References 180
10. Developing Molecular Copper Complexes for Water Oxidation 187
Shoshanna M. Barnett, Christopher R. Waidmann, Margaret L. Scheuermann, Jared C. Nesvet, Karen Goldberg and James M. Mayer
10.1 Introduction 187
10.2 A Biomimetic Approach 188
10.2.1 Thermochemistry: Developing Oxidant/Base Combinations as PCET Reagents 189
10.2.2 Copper Complexes with Alkylamine Ligands 190
10.2.3 Copper Complexes with Anionic Ligands 195
10.2.4 Lessons Learned: Thermochemical Insights and Oxidant/Base Compatibility 198
10.3 An Aqueous System: Electrocatalysis with (bpy)Cu(II) Complexes 198
10.3.1 System Selection: bpy + Cu 199
10.3.2 Observing Electrocatalysis 199
10.3.3 Catalyst Turnover Number and Turnover Frequency 201
10.3.4 Catalyst Speciation: Monomer, Dimer, or Nanoparticles? 203
10.4 Conclusion 206
Acknowledgement 206
References 207
11. Polyoxometalate Water Oxidation Catalytic Systems 211
Jordan M. Sumliner, James W. Vickers, Hongjin Lv, Yurii V. Geletii, and
Craig L. Hill
11.1 Introduction 211
11.2 Recent POM WOCs 214
11.3 Assessing POM WOC Reactivity 220
11.4 The Ru(bpy)3 2+ ?S2O8 2-System 221
11.5 Ru(bpy) 3 3+ as an Oxidant for POM WOCs 222
11.6 Additional Aspects of WOC System Stability 224
11.7 Techniques for Assessing POM WOC Stability 224
11.8 Conclusion 227
Acknowledgments 228
References 228
12. Quantum Chemical Characterization of Water Oxidation Catalysts 233
Pere Miro, Mehmed Z. Ertem, Laura Gagliardi, and Christopher J. Cramer
12.1 Introduction 233
12.2 Computational Details 235
12.2.1 Density Functional Theory Calculations 235
12.2.2 Multiconfigurational Calculations 236
12.3 Methodology 237
12.3.1 Solvation and Standard Reduction Potentials 237
12.3.2 Multideterminantal State Energies 238
12.4 Water Oxidation Catalysts 238
12.4.1 Ruthenium-Based Catalysts 238
12.4.2 Cobalt-Based Catalysts 245
12.4.3 Iron-Based Catalysts 248
12.5 Conclusion 251
References 252
Index 257
