Advances in Inorganic Chemistry (eBook)

Front Cover 1
Advances in Inorganic Chemistry, Volume 40 4
Copyright Page 5
CONTENTS 6
Chapter 1. Bioinorganic Chemistry of Pterin-Containing Molybdenum and Tungsten Enzymes 10
I. Scope and Overview 11
II. The Molybdenum Cofactor (Mo-co) 13
III. Coordination about the Molybdenum Atom 22
IV. Synthetic Models of the Molybdenum Centers 32
V. Reactions of Oxo-Molybdenum Centers 57
VI. The Xanthine Oxidase Cycle 70
VII. Intramolecular Electron Transfer in Molybdenum Enzymes 73
VIII. Pterin-Containing Tungsten Enzymes 79
IX. Future Directions 85
X. Abbreviations 86
References 87
Note Added in Proof 97
Chapter 2. Structure and Function of Nitrogenase 98
I. Introduction 98
II. Properties of the Nitrogenase Proteins 100
III. Structural Description of the Nitrogenase Proteins 104
IV. Structures of the Metal Centers of Nitrogenase 111
V. Mechanistic Features 116
VI. Future Outlook 125
References 126
Chapter 3. Blue Copper Oxidases 132
I. Introduction 132
II. Occurrence, Sequences, and Biological Function 134
III. Molecular and Spectroscopic Properties 136
IV. X-Ray Structure of Ascorbate Oxidase 139
V. Structural Relationships among the Blue Copper Oxidases 151
VI. Fungal Laccases, Ascorbate Oxidases, and Related Proteins 156
VII. Evolution of the Blue Oxidases and Related Proteins from a Common Ancestor 164
VIII. Oxidation–Reduction Potentials 166
IX. Kinetic Properties of Laccase and Ascorbate Oxidase 168
X. Functional Derivatives 183
XI. The Catalytic Mechanism 185
XII. Electron Transfer Processes 185
XIII. Summary 189
References 190
Chapter 4. Quadruply Bridged Dinuclear Complexes of Platinum, Palladium, and Nickel 198
I. Introduction 198
II. Preparation and Steric Structures 201
III. Spectroscopic Properties and Electronic Structures 232
IV. Redox Properties 240
V. Axial Ligand Substitution Properties 243
VI. Concluding Remarks 246
References 246
Chapter 5. Octacyano and Oxo- and Nitridotetracyano Complexes of Second and Third Series Early Transition Metals 252
I. Introduction 252
II. Octacyano Complexes 253
III. Tetracyano Complexes Containing Oxo or Nitrido Ligands 300
References 327
Chapter 6. Macrocyclic Complexes as Models for Nonporphine Metalloproteins 334
I. Scope 334
II. Introduction 335
III. Mononuclear Systems 338
IV. Dinuclear Sites 362
V. Polynuclear Active Sites 391
VI. Conclusion 410
References 410
Chapter 7. Complexes of Sterically Hindered Thiolate Ligands 422
I. Aim and Scope 422
II. Structures and Syntheses of Sterically Hindered Thiols 423
III. Transition Metal Complexes 426
IV. Main Group Complexes 460
V. Conclusions 461
References 463
Appendix: Summary Table of Sterically Hindered Thiolate Complexes 467
Index 472
Contents of Previous Volumes 484