List of Contributors ........................................... xi
Preface ........................................................ xv
1 Structural Studies of Oxomanganese Complexes for
Water Oxidation Catalysis .................................... 1
Ivan Rivaita, 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
[Ru2II(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 Crabtree2011 .......................................... 119
6.9 Crabtree2011 .......................................... 120
6.10 Lin 2011 .............................................. 120
6.11 Macchioni 2011 ........................................ 122
6.12 Grotjahn2011 .......................................... 123
6.13 Fukuzumi2011 .......................................... 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. Wickers, 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)32+/S2O82- System .......................... 221
11.5 Ru(bpy)33+ 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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