Preface ........................................................ XI
Foreword ..................................................... XIII
List of Contributors ........................................... XV
1 Gold(l) Nitrogen Chemistry ................................... 1
Hainan E. Abdou, Ahmed A. Mohamed, and John P. Fackler jr.
1.1 Introduction ............................................ 1
1.2 Tetra-, Tri-, and Dinuclear Gold(I) Amidinate
Complexes ............................................... 3
1.3 Oxidative-Addition Reactions to the Dinuclear Gold(I)
Amidinate Complex ....................................... 9
1.4 Mercury(II) Cyanide Coordination Polymer ............... 13
1.5 Formation of Mixed-Ligand Tetranuclear Gold(I)
Nitrogen Clusters ...................................... 15
1.6 Solvent Influences on Oxidation and Nuclearity of
Gold Guanidinate Derivatives ........................... 21
1.7 Cyclic Trinuclear Gold(I) Nitrogen Compounds ........... 24
1.8 Oxidative-Addition Reactions to the Cyclic Trinuclear
Gold(I)-Nitrogen Compounds ............................. 28
1.9 Supramolecular Entities of Trinuclear Gold(I)
Complexes Sandwiching Small Organic Acids .............. 30
1.10 Gold(I) and Silver(I) Mixed-Metal Trinuclear
Complexes .............................................. 33
1.11 CO Oxidation Over Au/TiO2 Prepared from Gold Nitrogen
Complexes .............................................. 36
1.12 Miscellaneous Observations ............................. 37
References .................................................. 37
2 Chemistry of Gold(lll) Complexes with Nitrogen and Oxygen
Ligands ..................................................... 47
Maria Agostina Cinellu
2.1 Introduction ........................................... 47
2.2 Nitrogen Donor Ligands ................................. 47
2.2.1 Complexes with Neutral Monodentate Ligands ...... 47
2.2.2 Complexes with Anionic Monodentate Ligands ...... 51
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 Cold 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
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 Cold - 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 ...... 286
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 Cold 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[5dσ*, 6рσ] 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
5.5 Concluding Remarks .................................... 274
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 Cold and Cold Surfaces ...................... 321
M.В. Cortie and A. McDonagh
7.1 Introduction .......................................... 321
7.2 Forms of Gold at the Nanoscale ........................ 323
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 ....................................... 340
7.4.7 Phosphorus, Arsenic, Antimony .................. 341
7.4.8 Carbon ......................................... 342
7.5 Conclusions ........................................... 342
References ................................................. 343
8 Liquid Crystals Based on Cold Compounds .................... 357
Siherio Coco and Pablo Espinet
8.1 Introduction .......................................... 357
8.1.1 A Few General Concepts in Liquid Crystals ...... 357
8.1.2 Gold, an Ideal Metal for LC Studies ............ 360
8.2 Pyridine Complexes .................................... 361
8.3 Dithiobenzoate Complexes .............................. 361
8.4 Isocyanide Complexes .................................. 362
8.4.1 Isocyanide-Halide Complexes .................... 362
8.4.2 Isocyanide-Alkynyl Complexes ................... 370
8.4.3 Isocyanide-Fluorophenyl Derivatives ............ 372
8.4.4 Ionic bis (isocyanide) Derivatives ............. 379
8.4.5 Mixtures: Liquid Crystalline "Molecular
Alloys" ........................................ 383
8.5 Carbene Complexes ..................................... 384
8.6 Complexes Containing Pyrazole-Type Ligands ............ 387
8.6.1 Trinuclear Gold Pyrazolate Rings:
Metallacrowns .................................. 387
8.6.2 "Mononuclear" Complexes ........................ 388
8.7 Ionic Imidazolium Derivatives ......................... 388
8.8 Liquid Crystalline Gold Nanoparticles ................. 388
Index ......................................................... 397
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