Gold Chemistry – Applications and Future Directions in the Life Sciences – Fabian Mohr (Wiley-VCH, 2009) (informative)
Free download Gold Chemistry – Applications and Future Directions in the Life Sciences – Fabian Mohr (Wiley-VCH, 2009)
Authors of: Gold Chemistry – Applications and Future Directions in the Life Sciences – Fabian Mohr (Wiley-VCH, 2009)
Fabian Mohr
Table of Contents in Gold Chemistry – Applications and Future Directions in the Life Sciences – Fabian Mohr (Wiley-VCH, 2009)
Preface XI
Foreword XIII
List of Contributors XV
1 Gold(I) Nitrogen Chemistry 1
Hanan E. Abdou, Ahmed A. Mohamed, and John P. Fackler Jr
1.1 Introduction
1.2 Tetra-, Tri-, and Dinuclear Gold(I) Amidinate Complexes
1.3 Oxidative-Addition Reactions to the Dinuclear Gold(I) Amidinate
Complex
1.4 Mercury(II) Cyanide Coordination Polymer
1.5 Formation of Mixed-Ligand Tetranuclear Gold(I) Nitrogen Clusters
1.6 Solvent Influences on Oxidation and Nuclearity of Gold
Guanidinate Derivatives
1.7 Cyclic Trinuclear Gold(I) Nitrogen Compounds
1.8 Oxidative-Addition Reactions to the Cyclic Trinuclear Gold(I)-Nitrogen
Compounds
1.9 Supramolecular Entities of Trinuclear Gold(I) Complexes
Sandwiching Small Organic Acids
1.10 Gold(I) and Silver(I) Mixed-Metal Trinuclear Complexes
1.11 CO Oxidation Over Au/TiO2 Prepared from Gold Nitrogen
Complexes
1.12 Miscellaneous Observations
References
2 Chemistry of Gold(III) Complexes with Nitrogen and Oxygen Ligands
Maria Agostina Cinellu
2.1 Introduction
2.2 Nitrogen Donor Ligands
2.2.1 Complexes with Neutral Monodentate Ligands
2.2.2 Complexes with Anionic Monodentate Ligands 51
V
2.2.3 Complexes with Multidentate Ligands 53
2.2.4 Complexes with Multidentate Ligands Containing
Anionic N-Donors 59
2.2.5 Complexes with Polyazamacrocyclic Ligands 63
2.3 Oxygen Donor Ligands 65
2.3.1 Hydroxo Complexes 65
2.3.2 Oxo Complexes 69
2.3.3 Alkoxo Complexes 72
2.3.4 Complexes With Other O-donor Ligands 76
2.3.5 Complexes With Mixed N/O Ligands 78
References 80
3 Pentafluorophenyl Gold Complexes 93
A. Luquin, E. Cerrada, and M. Laguna
3.1 Introduction 93
3.2 Pentafluorophenylgold(I) Derivatives 94
3.2.1 Neutral Pentafluorophenylgold(I) Derivatives 95
3.2.1.1 Neutral Pentafluorophenylgold(I) Derivatives with C-Donor Ligands 97
3.2.1.2 Neutral Pentafluorophenylgold(I) Derivatives
with N-Donor Ligands 100
3.2.1.3 Neutral Pentafluorophenylgold(I) Derivatives
with P-Donor Ligands 101
3.2.1.4 Neutral Pentafluorophenylgold(I) Derivatives
with S-Donor Ligands 102
3.2.2 Anionic Pentafluorophenylgold(I) Derivatives 103
3.2.2.1 Reactivity of the Anionic Pentafluorophenylgold(I) Complexes
Q[Au(C6F5)X] 105
3.2.3 Cationic Pentafluorophenylgold(I) Derivatives 107
3.2.4 Di and Polynuclear Pentafluorophenylgold(I) Derivatives 108
3.2.5 Heteronuclear Pentafluorophenylgold(I) Complexes 117
3.2.5.1 Heteronuclear Pentafluorophenylgold(I) Bismuth
Complexes 117
3.2.5.2 Heteronuclear Pentafluorophenylgold(I) Tin Complexes 117
3.2.5.3 Heteronuclear Pentafluorophenylgold(I) Thallium
Complexes 117
3.2.5.4 Heteronuclear Pentafluorophenylgold(I) Silver Complexes 119
3.2.5.5 Heteronuclear Pentafluorophenylgold(I) Copper Complexes 122
3.2.5.6 Heteronuclear Pentafluorophenylgold(I) Palladium
Complexes 122
3.2.5.7 Heteronuclear Pentafluorophenylgold(I) Rhodium Complexes 123
3.2.5.8 Heteronuclear Pentafluorophenylgold(I) Iron Complexes 123
3.2.5.9 Heteronuclear pentafluorophenylgold(I) manganese complexes 126
3.2.5.10 Heteronuclear Pentafluorophenylgold(I) Chromium, Gold
Molybdenum and Gold Tunsten Complexes 126
3.3 Pentafluorophenylgold(III) Derivatives 127
VI Contents
3.3.1 Mononuclear Pentafluorophenylgold (III) Derivatives 130
3.3.2 Di and Polynuclear Pentafluorophenylgold(III) Derivatives 138
3.3.2.1 C-Donor Ligands 138
3.3.2.2 Diamine and Carbene Bridges 143
3.3.2.3 N-, P- and As-Donor Ligands 143
3.3.2.4 S- and Se-Donor Ligands 147
3.3.3 Polynuclear Pentafluorophenylgold Derivatives with
Au(I)-Au(III) Bond 148
3.3.4 Heteropolynuclear Pentafluorophenylgold(III) Derivatives 149
3.3.5 Pentafluorophenylgold(III) Derivatives as Catalyst 150
3.4 Gold Clusters 155
3.5 Pentafluorophenylgold(II) Derivatives 156
3.5.1 Dinuclear Pentafluorophenylgold(II) Complexes 156
3.5.2 Polynuclear Pentafluorophenylgold(II) Complexes 159
3.6 Outlook and Future Trends 162
References 163
4 Theoretical Chemistry of Gold – From Atoms to Molecules,
Clusters, Surfaces and the Solid State 183
Peter Schwerdtfeger and Matthias Lein
4.1 Introduction 183
4.2 The Origin of the Relativistic Maximum at Gold Along the 6th
Period of Elements in the Periodic Table 186
4.3 Calculations on Atomic Gold 189
4.4 Relativistic Methods for Molecular Calculations and Diatomic
Gold Compounds 194
4.5 Calculations on Inorganic and Organometallic Gold Compounds 203
4.6 Calculations on Gold Clusters 212
4.7 Calculations on Infinite Systems: from Surfaces to the
Solid State of Gold 216
4.8 Summary 220
References 221
5 Luminescence and Photophysics of Gold Complexes 249
Chi-Ming Che and Siu-Wai Lai
5.1 Introduction 249
5.2 Spectroscopic Properties of Gold(I) Complexes 250
5.2.1 Mononuclear Gold(I) Complexes 250
5.2.2 Di- and Polynuclear Gold(I) Complexes with Metal–Metal
Interactions 252
5.2.3 High-Energy 3
[5ds , 6ps] Excited State Versus Visible
Metal-Anion/Solvent Exciplex Emission 262
5.2.4 Chemosensory Applications 267
5.3 Spectroscopic Properties of Gold(III) Complexes 270
5.4 Photoinduced Electron Transfer Reactions of Gold Complexes 273
Contents VII
5.5 Concluding Remarks 274
References 276
6 Gold Compounds and Their Applications in Medicine 283
Elizabeth A. Pacheco, Edward R.T. Tiekink, and Michael W. Whitehouse
6.1 Introduction 283
6.2 The Aqueous Chemistry of Gold Compounds 283
6.2.1 Structures of Gold(I) and Gold(III) Complexes 284
6.2.2 Oxidation–Reduction Reactions 284
6.2.3 Ligand Exchange Mechanisms 285
6.3 Medicinally Important Gold Complexes, Their Analogs
and Reactions 287
6.3.1 Oligomeric Gold(I) Thiolates and Analogs 287
6.3.2 Bis(thiolato)Gold(I) Species 290
6.3.3 Dithiocarbamates 291
6.3.4 Auranofin and Other Phosphine(Thiolato)Gold(I) Species 291
6.3.5 Au–S Bond Length Comparisons 292
6.3.6 Complexes of Diphosphine Ligands 293
6.3.7 Gold(I) Cyanide Complexes 294
6.3.8 Heterocyclic Carbenes 295
6.4 Gold–Protein Reactions and Complexes 295
6.4.1 Serum Albumin 295
6.4.2 Metallothioneins 297
6.4.3 Selenium-Dependent Glutathione Peroxidase 300
6.4.4 Gold(III) Oxidation of Insulin and Ribonuclease 301
6.4.5 Enzyme Inhibition 301
6.4.6 Zinc finger Proteins 302
6.4.7 Hemoglobin and Interprotein Gold Transfer (‘‘Transauration’’) 303
6.4.8 Mitochondrial Thioredoxin Reductase 303
6.5 Physiological and Cellular Biochemistry 304
6.5.1 Biological Ligand Exchange 304
6.5.2 The Sulfhydryl-Shuttle Model 305
6.5.3 Equilibration of Intra- and Extracellular Gold 305
6.5.4 Cytotoxicity and Antitumor Activity of Gold Complexes 306
6.5.5 Oxidation States in Vivo 307
6.5.6 Immunochemical Consequences of Gold(III) 308
6.5.7 Anti-HIV Activity 308
6.5.8 Gold Nanoparticles 309
6.6 Conclusions 309
References 310
7 Nanoscience of Gold and Gold Surfaces 321
M.B Cortie and A. McDonagh
7.1 Introduction 321
7.2 Forms of Gold at the Nanoscale 323
VIII Contents
7.2.1 Clusters and Nanoparticles of Less than 5 nm Diameter 323
7.2.2 Nanospheres 325
7.2.3 Nanoshells 325
7.2.4 Nanorods 327
7.2.5 Other Nanoparticle Shapes 327
7.2.6 Mesoporous Sponges 327
7.2.7 Thin Films 329
7.2.8 Assemblages of Nanoparticles 330
7.2.8.1 Disordered Aggregates 330
7.2.8.2 Colloidal Crystals 330
7.3 Onset of New Phenomena 331
7.3.1 Optical 331
7.3.1.1 The Plasmon Resonance 331
7.3.1.2 Manipulation of the Plasmon Resonance 332
7.3.1.3 Fluorescence and Luminescence 333
7.3.2 Physical 334
7.3.2.1 Depression of the Melting Point 334
7.3.3 Chemical 334
7.3.3.1 Heterogeneous Catalysis 334
7.4 Surface Chemistry of Gold 335
7.4.1 Hydrogen 335
7.4.2 Halogens 336
7.4.3 Oxygen 337
7.4.4 Sulfur 338
7.4.4.1 Isothiocyanates 339
7.4.5 Selenium and Tellurium 339
7.4.6 Nitrogen
7.4.7 Phosphorus, Arsenic, Antimony
7.4.8 Carbon
7.5 Conclusions
References
8 Liquid Crystals Based on Gold Compounds
Silverio Coco and Pablo Espinet
8.1 Introduction
8.1.1 A Few General Concepts in Liquid Crystals
8.1.2 Gold, an Ideal Metal for LC Studies
8.2 Pyridine Complexes
8.3 Dithiobenzoate Complexes
8.4 Isocyanide Complexes
8.4.1 Isocyanide-Halide Complexes
8.4.2 Isocyanide-Alkynyl Complexes
8.4.3 Isocyanide-Fluorophenyl Derivatives
8.4.4 Ionic bis(isocyanide) Derivatives
8.4.5 Mixtures: Liquid Crystalline ‘‘Molecular Alloys’’
8.5 Carbene Complexes
8.6 Complexes Containing Pyrazole-Type Ligands
8.6.1 Trinuclear Gold Pyrazolate Rings: Metallacrowns
8.6.2 ‘‘Mononuclear’’ Complexes
8.7 Ionic Imidazolium Derivatives
8.8 Liquid Crystalline Gold Nanoparticles
8.9 Conclusions
References
Index
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