Advances in Inorganic Chemistry (eBook)

Cover 1
Contents 6
Preface 10
Chapter 1. Synergy Between Theory and Experiment as Applied to H/D Exchange Activity Assays in [Fe]H2ase Active Site Models 12
I. Introduction 12
II. Experimental Section 15
III. Results and Discussion 17
IV. Conclusions 34
References 35
Chapter 2. Electronic Structure and Spectroscopic Properties of Molybdenum and Tungsten N2, NNH, NNH2, and NNH3 Complexes With Diphosphine co-ligands: Insights into the End-On Terminal Reduction Pathway of Dinitrogen 38
I. Introduction 38
II. Vibrational Spectroscopy and QCA-NCA 41
III. Electronic Structure and Electronic Absorption Spectroscopy 54
IV. Conclusions 61
References 63
Chapter 3. Quantum Chemical Investigations into the Problem of Biological Nitrogen Fixation: Sellmann-Type Metal–Sulfur Model Complexes 66
I. Introduction 67
II. The Active Site of Nitrogenase: FeMo-Cofactor 68
III. Biomimetic Sellmann-Type Metal Complexes 72
IV. The First 2-Electron–2-Proton Transfer 75
V. Reaction Energetics of the Reduction at Mononuclear Fe(II) Centers 85
VI. Photoisomerization of Coordinated Diazene 93
VII. Study of the First Dinuclear N2 Complex with Biologically Compatible Ligand Sphere 99
VIII. Conclusion 103
IX. Appendix: Quantum ChemicalMethodology 104
References 108
Chapter 4. Proton and Electron Transfers in [NiFe] Hydrogenase 112
I. Introduction 112
II. Computational Details 115
III. Results and Discussion 116
IV. Conclusions 134
References 134
Chapter 5. Heterolytic Splitting of H–H, Si–H, and Other s Bonds on Electrophilic Metal Centers 138
I. Introduction 138
II. Heterolytic Cleavage and Acidity of Coordinated H2 143
III. Heterolytic Cleavage of Si–H Bonds 161
IV. Heterolytic Cleavage of B–H and C–H Bonds 179
V. Concluding Remarks 182
References 184
Chapter 6. Tetrapodal Pentadentate Nitrogen Ligands: Aspects of Complex Structure and Reactivity 190
I. Introduction 190
II. Overview 191
III. Tetrapodal Pentadentate CoordinationModules 194
IV. Conclusion 217
References 217
Chapter 7. Efficient, Ecologically Benign, Aerobic Oxidation of Alcohols 222
I. Introduction 223
II. First Generation Copper-Catalyzed Aerobic Oxidation Protocol 223
III. Second Generation Copper-Catalyzed Aerobic Oxidation Protocol 227
IV. Third Generation Copper-Catalyzed Aerobic Oxidation Protocol 234
V. Towards aTruly Eficient, Aerobic, Catalytic Oxidation Protocol 239
References 247
Chapter 8. Visible Light Photocatalysis by a Titania Transition Metal Complex 252
I. Introduction 252
II. Preparation and Characterization of Photocatalysts 253
III. Photocatalytic Degradation with Artificial Visible Light (l 355nm) 260
IV. Photodegradation with Natural Indoor Daylight 263
V. Photodegradation with Sunlight 264
VI. Mechanism 265
VII. Summary 269
References 269
INDEX 272
CONTENTS OF PREVIOUS VOLUMES 280