Advances in Inorganic Chemistry (eBook)

Front cover 1
Advances in Inorganic Chemistry 4
Copyright page 5
Contents 6
List of Contributors 10
Preface 12
Chapter 1. Controlling platinum, ruthenium, and osmium reactivity for anticancer drug design 14
I. Introduction 14
II. Platinum Anticancer Prodrugs: A Photoactivation Strategy 17
III. Ruthenium-Arene Anticancer Drugs 34
IV. Osmium(II)-Arenes: A Cytotoxic Family of the Heavier Congener 64
V. Concluding Remarks 70
Acknowledgments 71
References 71
Chapter 2. Design and function of metal complexes as contrast agents in MRI 76
I. Introduction 76
II. Relaxivity of GdIII Complexes: Optimization of the Relaxivity 80
III. Stability Aspects 105
IV. Paramagnetic CEST Agents 111
V. Responsive Imaging Probes 114
VI. MnII Complexes in the Context of MRI 122
VII. Non-Classical GdIII-Based MRI Contrast Agents 128
VIII. Conclusions and Outlook 132
References 132
Chapter 3. Design considerations towards simultaneously radiolabeled and fluorescent imaging probes incorporating metallic species 144
I. Introduction 144
II. Small-Molecule Metal-Based Probes and Their Biomedical Imaging Capabilities 150
III. Conclusions 184
Acknowledgments 185
References 185
Chapter 4 .Iron sequestration by small molecules: Thermodynamic and kinetic studies of natural siderophores and synthetic model compounds 192
I. Chemistry of Iron and Siderophores 192
II. Siderophore Structure 195
III. Thermodynamics of Iron-Siderophore Interactions 199
IV. Chelation Kinetics of Iron-Siderophore Systems 233
V. Siderophore Recognition and Cellular Uptake 244
VI. Applications and Future Directions in Siderophore Research 248
List of Structure Numbers, Figures, and Abbreviations 253
Acknowledgments 255
References 255
Chapter 5. Calcium in biological systems 264
I. Introduction 265
II. The Ca2plus Aqua-Cation 281
III. Calcium-Binding Metalloproteins 302
IV. Ca2plus in Ionophores, Channels, and Pumps 321
V. Carbohydrates and Carboxylates 329
VI. Phosphates, Phosphonates, Nucleosides, and Nucleotides 334
VII. Stability Constants: An Overview 339
VIII. Calcium-Containing Rigid Materials 339
Ligand Abbreviations 351
Acknowledgments 352
References 352
Appendix: The Term Ligand 378
Chapter 6. New developments in synthetic nitrogen fixation with molybdenum and tungsten phosphine complexes 380
I. Introduction 380
II. Mechanism of the Chatt Cycle: Experimental Investigations 384
III. Mechanism of the Chatt Cycle: Theoretical Investigations 395
IV. Molybdenum Dinitrogen Complexes with Polydentate Phosphine and Mixed PsolN Ligands 399
V. Conclusions 414
Acknowledgments 415
References 415
Chapter 7. Chemistry of metalated container molecules 420
I. Introduction 420
II. Metalated Container Molecules: Host Systems and Complex Types 422
II. Metalated Container Molecules of Binucleating Polyaza-Dithiophenolate Macrocycles 443
IV. Conclusion 470
Acknowledgments 471
References 471
Chapter 8. Mechanistic considerations on the reactivity of green FeIII-TAML activators of peroxides 484
I. Introduction 485
II. Speciation of Tetraamide Iron(III) Macrocycles in Solution and the Solid State 486
III. Kinetics and Mechanisms of Demetalation of FeIII-TAML Activators 491
IV. Catalysis-Relevant Oxidized Forms Derived from FeIII-TAMLs 500
V. Mechanism of Catalysis by Tetraamide Macrocyclic FeIII-TAML Activators of Hydrogen Peroxide, Functional Catalase-Peroxidase Replicas 507
VI. The Activity-Stability Parameterization of Homogeneous Green Oxidation Catalysts 523
VII. Concluding Remarks 529
Acknowledgment 530
References 530
Chapter 9. Ligand exchange processes on the smallest solvated alkali and alkaline earth metal cations: An experimental and theoretical approach 536
I. Introduction 536
II. Solvation of Metal Ions 539
III. Solvent Exchange Mechanism 546
IV. Conclusion 577
Acknowledgments 577
References 577
Chapter 10. Spin-state changes and reactivity in transition metal chemistry: Reactivity of iron tetracarbonyl 586
I. Introduction 586
II. Chemistry of Fe(CO)5 Photofragments 590
III. Other Spin-Forbidden Reactions of Transition Metal Compounds 619
IV. Spin-Forbidden Reactions: General Trends 622
V. Conclusions 629
Acknowledgments 631
References 631
Index 638
Contents of previous volumes 662