The first to combine both the bioinorganic and the organometallic view, this handbook provides all the necessary knowledge in one convenient volume. Alongside a look at CO2 and N2 reduction, the authors discuss O2, NO and N2O binding and reduction, activation of H2 and the oxidation catalysis of O2.
Edited by the highly renowned William Tolman, who has won several awards for his research in the field.
Preface XIII
List of Contributors XV
1 Carbon Dioxide Reduction and Uses as a Chemical Feedstock 1
Michele Aresta
1.1 Introduction 1
1.2 Properties of the CO2 Molecule 3
1.2.1 Molecular Geometry 3
1.2.2 Spectroscopic Properties 3
1.2.3 Energy Data and Reaction Kinetics Relevant to CO2 Conversion 5
1.3 CO2 Coordination to Metal Centers and Reactivity of Coordinated CO2 6
1.3.1 Modes of Coordination 6
1.3.2 Interaction of CO2 with Metal Atoms at Low Temperature: Stability of the Adducts 8
1.3.3 Reactivity of CO2 Coordinated to Transition Metal Systems 8
1.4 CO2 Conversion 9
1.4.1 Carboxylation Reactions 10
1.4.2 Reduction Reactions 28
1.5 Conclusions 34
References 35
2 Nitrogen Monoxide and Nitrous Oxide Binding and Reduction 43
Dong-Heon Lee, Biplab Mondal, and Kenneth D. Karlin
2.1 Introduction 43
2.2 NO 44
2.2.1 Bonding and Structures of Metal Nitrosyls 44
2.2.2 Chemical Reduction of NO and Related Chemistry 53
2.3 N2O 66
2.3.1 Structure and Bonding 66
2.3.2 Metal-mediated N2O Reduction 68
2.4 Summary and Conclusions 73
References 74
3 Bio-organometallic Approaches to Nitrogen Fixation Chemistry 81
Jonas C. Peters and Mark P. Mehn
3.1 Introduction The N2 Fixation Challenge 81
3.2 Biological N2 Reduction 83
3.2.1 General Comments 83
3.2.2 Structural Data 84
3.2.3 Assigning the FeMoco Oxidation States 85
3.3 Biomimetic Systems that Model Structure and Function 86
3.3.1 General Comments 86
3.3.2 Mononuclear Molybdenum Systems of Biomimetic Interest 86
3.3.3 Considering Mechanisms Involving Multiple and Single Iron Sites for N2 Reduction 96
3.4 Concluding Remarks 115
References 116
4 The Activation of Dihydrogen 121
Jesse W. Tye and Michael B. Hall
4.1 Introduction 121
4.1.1 Why Activate H2? 121
4.1.2 Why is it so Difficult to Activate H2? 122
4.2 Structure and Bonding of Metal-bound H-Atoms 124
4.2.1 Why can Metal Centers React Directly with H2, while most Nonmetals Cannot? 124
4.2.2 Seminal Work: The Discovery of Metal-bound H2 Complexes 125
4.2.3 What are the Possible Consequences when H2 Approaches a Coordinatively Unsaturated Transition Metal Center? 126
4.2.4 Elongated _2-H2 Complexes 128
4.2.5 Experimental Gauges of the HH Interaction and Degree of Activation 129
4.3 Intramolecular H-Atom Exchange 131
4.3.1 Rotation of 2-H Ligands 132
4.3.2 H2/H Exchange 134
4.3.3 HydrideHydride Exchange 135
4.4 Nonclassical H-Bonds 136
4.4.1 Hydride Ligands as Nonclassical H-Bond Acceptors 136
4.4.2 2-H2 as a Nonclassical H-Bond Donor 136
4.5 Reactivity of Metal-bound H-Atoms 137
4.5.1 How Does the Reactivity of Metal-bound H-atoms Compare to that of Free H2? 137
4.5.2 Metal-Monohydride Species Hydride Ligands can be Acidic! 138
4.5.3 Increased Acidity of 2-H2 139
4.5.4 Seminal Work: Intramolecular Heterolytic Cleavage of H2 141
4.6 Recent Advances in the Activation of Dihydrogen by Synthetic Complexes 141
4.6.1 H2 Uptake by a PtRe Cluster 141
4.6.2 H2 Binding to IrIII Initiates Conversion of CF3 to CO 142
4.6.3 Encapsulation of H2 in C60 142
4.6.4 Conversion of Biomass to H2 142
4.6.5 First Group 5 2-H2 Complex 142
4.7 Enzymatically Catalyzed Dihydrogen Oxidation and Proton Reduction 142
4.7.1 General Information about H2ase Enzymes 143
4.7.2 H2 Production by N2ase 148
4.8 Conclusions 149
Acknowledgments 150
Abbreviations 150
References 150
5 Molecular Oxygen Binding and Activation: Oxidation Catalysis 159
Candace N. Cornell and Matthew S. Sigman
5.1 Introduction 159
5.2 Additive Coreductants 161
5.2.1 Aldehydes 161
5.2.2 Coupled Catalytic Systems 165
5.3 Ligand-modified Catalysis 170
5.3.1 Porphyrin Catalysis 171
5.3.2 Schiff Bases 172
5.3.3 Nitrogen-based Ligands 176
5.3.4 Other Ligand Systems 180
5.4 Conclusions and Outlook 182
References 183
6 Dioxygen Binding and Activation: Reactive Intermediates 187
Andrew S. Borovik, Paul J. Zinn and Matthew K. Zart
6.1 Introduction 187
6.1.1 An Example: Cytochromes P450 188
6.1.2 Effective O2 Binders and Activators in Biology 191
6.2 Dioxygen Binders 192
6.2.1 Respiratory Proteins 192
6.2.2 Synthetic Analogs 194
6.3 Reactive Intermediates: Iron and Copper Species 207
6.3.1 Reactive Species with Fe-oxo Motifs 208
6.3.2 Reactive Iron and Copper Intermediates with M(_-O)2M Motifs 215
6.4 CobaltDioxygen Complexes 221
6.4.1 Cobalt-2-Dioxygen Complexes 221
6.4.2 Dinuclear Cobalt--superoxo Complexes 222
6.5 ManganeseDioxygen Complexes 225
6.6 NickelDioxygen Complexes and Their Reactive Intermediates 227
6.7 Summary 229
Acknowledgments 229
References 229
7 Methane Functionalization 235
Brian Conley, William J. Tenn, III, Kenneth J.H. Young, Somesh Ganesh, Steve Meier, Jonas Oxgaard, Jason Gonzales, William A. Goddard, III, and Roy A. Periana
7.1 Methane as a Replacement for Petroleum 235
7.2 Low Temperature is Key to Economical Methane Functionalization 237
7.2.1 Lower Temperature Leads to Lower Costs 237
7.2.2 Methane Functionalization by CH Hydroxylation 238
7.2.3 Methane as the Least Expensive Reductant on the Planet 238
7.2.4 Selectivity is the Key to Methane Functionalization by CH Hydroxylation 240
7.2.5 Requirements of Methane Functionalization Chemistry Influenced by Plant Design 241
7.2.6 Strategy for Methane Hydroxylation Catalyst Design 244
7.3 CH Activation as a Pathway to Economical Methane Functionalization via CH Hydroxylation 245
7.3.1 CH Activation is a Selective, Coordination Reaction 245
7.3.2 Comparison of CH Activation to Other Alkane Coordination Reactions 248
7.3.3 Some Key Challenges and Approaches to Designing Hydroxylation Catalysts Based on the CH Activation Reaction 253
7.4 Conclusions and Perspective for Methane Functionalization 282
References 283
8 Water Activation: Catalytic Hydrolysis 287
Lisa M. Berreau
8.1 Introduction 287
8.1.1 Water Activation 287
8.1.2 Catalytic Hydrolysis 287
8.2 Water Activation: Coordination Sphere Effects on M-OH2 Acidity and Structure 288
8.2.1 Primary Coordination Environment 288
8.2.2 Secondary H-Bonding 293
8.2.3 Intramolecular H-Bonding and Mononuclear Zn-OH Stabilization 297
8.2.4 Structural Effects Derived from M-OH2 Acting as an Intramolecular H-Bond Donor to a Bound Phosphate Ester 298
8.2.5 Ligand Effects on the pKa of a Metal-bound Water in Co(III) and Fe(III) Complexes 299
8.2.6 Acidity and Water Exchange Properties of Organometallic Aqua Ions 300
8.3 Secondary H-Bonding Effects on Substrate Coordination, Activation and Catalytic Hydrolysis Involving Phosphate Esters 302
8.3.1 H-Bonding and Phosphate Ester Coordination to a Metal Center 302
8.3.2 H-Bonding and Stochiometric and Catalytic Phosphate Ester Hydrolysis 304
8.4 Summary and Future Directions 312
References 314
9 Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis 319
Piet W.N.M. van Leeuwen and Zoraida Freixa
9.1 Introduction 319
9.1.1 Heterogeneous Processes 319
9.1.2 Homogeneous Catalysts 321
9.2 Rhodium-catalyzed Hydroformylation 322
9.2.1 Introduction 322
9.2.2 CO as the Ligand 323
9.2.3 Phosphites as Ligands 324
9.2.4 Arylphosphines as Ligands 328
9.2.5 Alkylphosphines as Ligands 337
9.3 Methanol Carbonylation 339
9.3.1 Introduction 339
9.3.2 Mechanism and Side-reactions of the Monsanto Process 340
9.3.3 Oxidative Addition of MeI to Rhodium The Rate-limiting Step 342
9.3.4 Ligand Design 344
9.3.5 Trans-diphosphines in Methanol Carbonylation Dinuclear Systems? 347
9.3.6 Iridium Catalysts 349
9.4 Concluding Remarks 351
References 351
Subject Index 357
