Professor Dr. Antoni Llobet, Institute of Chemical Research of Catalonia (ICIQ) and Universitat Autònoma de Barcelona, Spain
Professor Llobet is one of the world leaders on water oxidation catalysis. He has been working in the field of redox catalysis for 25 years; his research interests include the development of tailored transition metal complexes as catalysts for selective organic and inorganic transformations including the oxidation of water to molecular dioxygen, supramolecular catalysis, the activation of C-H and C-F bonds, and the preparation low molecular weight complexes as models of the active sites of oxidative metalloproteins.
In 2000, Professor Llobet received the Distinction Award from Generalitat de Catalunya for Young Scientists and in 2011 he was awarded the Bruker Prize in Inorganic Chemistry from the Spanish Royal Society of Chemistry (RSEQ). He is the author of over 120 research publications.

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 Francàs, Roger Bofill, Jordi García-Antón, 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 [Ru^II₂ (𝜇-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-𝜇-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 Miró, 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

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