Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine II (Structure and Bonding Book 154)

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Preface 6 Contents 10 Ambivalent Lewis Acid/Bases with Symmetry Signatures and Isolobal Analogies 11 1 Introduction 12 2 Ligands with Symmetry Signatures 19 2.1 Ambivalent Ligands 19 2.2 Ambiphilic Ligands 25 2.3 Ambiphilic and Ambivalent Metal Complexes 30 2.4 Valence Tautomerism 35 2.5 π-Bonded Alternative Geometries 36 2.6 Summary 38 3 Isolobal Analogies for Nitrosyl Complexes 39 3.1 Introduction 39 3.2 Theoretical Underpinning of the Isolobal Analogy 45 3.3 Sixteen-Electron Isolobal Analogies 48 3.4 Isolobal Analogies for Bent Nitrosyl Complexes 49 3.5 Isolobal 19-Electron Complexes 51 3.6 Trans-Influences in Isolobal Complexes 53 3.7 Isolobal Poly(Nitrosyls) and Poly-Nitrido-Oxo and Imido Complexes 55 3.8 Summary 56 References 58 The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes 62 1 Introduction 63 2 Dinitrosyl Complexes Containing a Single Metal Center 64 2.1 Dicarbonyldinitrosyl Iron 64 2.2 Phosphorus Based Ligands 65 2.3 Nitrogen-Based Ligands 73 3 Nitrosyl Complexes Containing Two or More Metal Centers 79 3.1 Complexes Containing ``M2S2 ́ ́ Core 79 3.2 Iron-Sulfur and Iron-Selenium Nitrosyl Clusters 89 3.3 Multinuclear Metal Nitrosyl Complexes 94 4 Mononitrosyl and Trinitrosyl Complexes 96 4.1 Mononitrosyl Complexes: 96 4.2 Trinitrosyl Complexes 101 5 Organometallic Metal Nitrosyl Complexes 101 6 Conclusion 102 References 104 Mechanisms of Nitric Oxide Reactions Mediated by Biologically Relevant Metal Centers 108 1 Introduction 110 2 Metal-Nitrosyl Bonding 110 3 How Does the Coordinated Nitrosyl Affect the Metal Center? 113 4 The Formation and Decay of Metal Nitrosyls 116 4.1 Some General Considerations 116 4.2 Rates of NO Reactions with Hemes and Heme Models 119 4.3 Mechanistic Studies of NO ``On ́ ́ and ``Off ́ ́ Reactions with Hemes and Heme Models 124 4.4 Non-Heme Iron Complexes 125 4.5 Other Metal Centers of Biological Interest 127 5 Reductive Nitrosylation and Other Reactions of Coordinated NO 129 5.1 Reactions of Iron(III) Nitrosyls with Nucleophiles 130 5.2 Reduction of Copper(II) Complexes by NO 131 5.3 Protonation of Metal Nitrosyls 136 5.4 Reactions with Dioxygen 137 6 Summary 139 References 140 Synthetic Models of Copper-Nitrosyl Species Proposed as Intermediates in Biological Denitrification 145 1 Introduction 146 2 [CuNO]11 Complexes 149 3 [CuNO]10 Complexes 152 4 [NiNO]10 Complexes 154 5 Summary, Conclusions, and Outlook 158 References 158 Structure and Bonding in Heme-Nitrosyl Complexes and Implications for Biology 162 1 Introduction 164 2 Geometric Structures of Heme-Nitrosyls 167 2.1 Ferrous Heme-Nitrosyls 167 2.1.1 Five-Coordinate Nitrosyls 167 2.1.2 Six-Coordinate Nitrosyls 171 2.2 Ferric Heme-Nitrosyls 176 2.3 Related Nitrosyls (Mn and Co) 180 3 Spectroscopic Properties of Heme-Nitrosyls 181 3.1 Ferrous Heme-Nitrosyls 181 3.1.1 Electron Paramagnetic Resonance 182 3.1.2 Vibrational Spectroscopy 186 3.1.3 General and Biological Implications 189 3.2 Ferric Heme-Nitrosyls 193 3.2.1 Vibrational Spectroscopy 194 3.2.2 The Effect of Axial Thiolate Ligation 195 3.2.3 Biological Implications 198 4 Electronic Structures of Heme-Nitrosyls 200 4.1 Ferrous Heme-Nitrosyls 200 4.1.1 Six-Coordinate Ferrous Heme-Nitrosyls 201 4.1.2 Experimental Insight into the Nature of the SOMO 204 4.1.3 Experimental Evaluation of the Spin Density Distribution 207 4.1.4 Electronic Structure Description of Ferrous-Heme Nitrosyls 208 4.1.5 Biological Implications 209 4.2 Ferric Heme-Nitrosyls 211 4.2.1 NO Binding to Ferric Heme: A Multidimensional Problem (See [54]) 212 4.2.2 Effect of Axial Thiolate and Other Anionic Ligand Coordination 214 4.2.3 Biological Implications 216 5 Ferrous Heme-Nitroxyl Complexes 217 6 Heme-Nitrosyl Complexes as Intermediates in Enzyme Catalysis: New Computational Insight 220 6.1 Fungal Nitric Oxide Reductase 220 6.2 Bacterial Nitric Oxide Reductase 222 6.3 Multiheme Cytochrome c Nitrite Reductase 224 7 Conclusions 225 References 225 Medical Applications of Solid Nitrosyl Complexes 231 1 Nitric Oxide in Biology 233 1.1 Endogenous Production of Nitric Oxide 235 1.2 Toxicity and Biological Activity of Nitric Oxide 236 1.3 Potential of Gasotransmitters as Therapeutics 237 2 Delivery of Nitric Oxide from Nitrosyl Complexes and Clusters 239 2.1 Gas Storage in Porous Materials 240 2.2 Methods of Gas Storage 241 2.3 Metal-Organic Frameworks 242 2.4 Synthesis and General Features 243 2.5 MOFs for Biological Applications 245 2.6 Porous Materials for Storage and Delivery of Nitric Oxide 245 2.7 Structural and Mechanistic Studies of Nitric Oxide Adsorption and Release 250 3 Looking Ahead: Other Gasotransmitter Molecules 251 3.1 Carbon Monoxide and Organ Transplantation 253 3.2 Hydrogen Sulfide and Suspended Animation 254 3.3 Interactions of the Gasotransmitters 254 4 General Implications and Future Directions 255 References 255 Index 263 D. Michael P. Mingos Ambivalent Lewis acid/bases with Symmetry Signatures and Isolobal Analogies Lauren R. Holloway, Lijuan Li The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes Peter C. Ford, Jose Clayston Melo Pereira and Katrina M. Miranda Mechanisms of Nitric Oxide Reactions Mediated by Biologically Relevant Metal Centers Debra J. Salmon, William B. Tolman Synthetic Models of Copper-Nitrosyl Species Proposed as Intermediates in Biological Denitrification Nicolai Lehnert, W. Robert Scheidt, Matthew W. Wolf Structure and Bonding in Heme-Nitrosyl Complexes and Implications for Biology Phoebe K. Allan, Russell E. Morris Medical Applications of Solid Nitrosyl Complexes Front Matter....Pages i-ix Ambivalent Lewis Acid/Bases with Symmetry Signatures and Isolobal Analogies....Pages 1-51 The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes....Pages 53-98 Mechanisms of Nitric Oxide Reactions Mediated by Biologically Relevant Metal Centers....Pages 99-135 Synthetic Models of Copper–Nitrosyl Species Proposed as Intermediates in Biological Denitrification....Pages 137-153 Structure and Bonding in Heme–Nitrosyl Complexes and Implications for Biology....Pages 155-223 Medical Applications of Solid Nitrosyl Complexes....Pages 225-256 Back Matter....Pages 257-260 D. Michael P. Mingos Historical Introduction to Nitrosyl Complexes Hanna Lewandowska Coordination Chemistry of Nitrosyls and Its Biochemical Implications Hanna Lewandowska Spectroscopic Characterization of Nitrosyl Complexes Yanfeng Jiang, Heinz Berke Nitrosyl Complexes in Homogeneous Catalysis