Contents. Preface XI Abbreviation XV List of Contributors XIX

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1 V Preface XI Abbreviation XV List of Contributors XIX 1 The Chemistry of Gold 1 M. Concepción Gimeno 1.1 Introduction History Chemical and Physical Properties Theoretical Considerations Chemistry Gold(-I) Compounds Gold(0) and Gold Clusters Gold Nanoparticles and Nanoclusters Gold(I) Complexes Mononuclear [AuXL], [AuL 2 ] þ or [AuX 2 ] Complexes Gold(I) Complexes with Polydentate Ligands Three and Four-Coordinate Gold(I) Complexes Oligomeric Gold(I) Complexes Single Heteroatom Bridged Gold(I) Complexes Organometallic Gold(I) Complexes Gold(II) Complexes Mononuclear Gold(II) Complexes Polynuclear Gold(II) Complexes Gold(III) Complexes Organometallic Gold(III) Complexes Gold(III) Complexes with Polydentate Ligands Gold(III) Complexes with Chalcogen Ligands Gold in Higher Oxidation States 49 References 50 Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna Copyright # 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN:

2 VI 2 Gold Gold Interactions 65 Olga Crespo 2.1 Introduction Gold(I) Gold(I) Interactions Aggregation of Mononuclear Dicoordinated Gold Units Dinuclear Aggregates Tri- and Tetranuclear Associations Formation of Infinite Chains and Supramolecular Arrays Clustering of Gold Atoms at One Center Complexes with Bridging Monodentate Ligands Complexes with Bridging Bidentate Ligands Complexes with Polydentate Ligands Gold(I)-Gold(III) Interactions Concluding Remarks 117 References Gold Nanomaterials 131 Eduardo J. Fernández and Miguel Monge 3.1 Introduction Molecular Gold Clusters Synthesis and Structural Characterization of Phosphine-Stabilized Gold Clusters Gold Clusters with Other Ligand Stabilizers Large-Size Gold Clusters. The Au 55 Case Gold Nanoparticles Synthesis of Gold Nanoparticles Monolayer Protected Clusters Other Ligands Polymers Dendrimers Seeded Growth Nanoparticle Biomolecule Hybrids Nanoparticle Assembly Properties and Applications of Gold Nanoparticles Concluding Remarks 172 References Gold Heterometal Interactions and Bonds 181 Cristian Silvestru 4.1 Introduction Main Group Metal Gold Compounds Gold Group 1 Metal Compounds Gold Mercury Compounds Gold Group 13 Metal Compounds Gold Gallium Compounds 192

3 VII Gold Indium Compounds Gold Thallium Compounds Gold Group 14 Metal Compounds Gold Silicon Compounds Gold Germanium Compounds Gold Tin Compounds Gold Lead Compounds Gold Group 15 Metal Compounds Gold Antimony Compounds Gold Bismuth Compounds Transition Metal Gold Compounds Gold Titanium Compounds Gold Group 5 Metal Compounds Gold Vanadium Compounds Gold Niobium Compounds Gold Group 6 Metal Compounds Gold Chromium Compounds Gold Molybdenum and Gold Tungsten Compounds Gold Group 7 Metal Compounds Gold Manganese and Gold Rhenium Compounds Gold Technetium Compounds Gold Group 8 Metal Compounds Gold Group 9 Metal Compounds Gold Group 10 Metal Compounds Gold Nickel Compounds Gold Palladium Compounds Gold Platinum Compounds Gold Group 11 Metal Compounds Gold Copper Compounds Gold Silver Compounds Concluding Remarks 272 References Supramolecular Architecture by Secondary Bonds 295 María Elena Olmos 5.1 Introduction Supramolecular Gold Entities Built with Gold Non-Metal Secondary Bonds Secondary Bonds: AuNM Interactions Hydrogen Bonds: AuH NM Interactions Aup Interactions Supramolecular Gold Entities Built with Non-Metal Non-Metal Secondary Bonds Secondary Bonds: NMNM Interactions Hydrogen Bonds: NMH NM Interactions 326

4 VIII C Hp Interactions and pp Stacking Concluding Remarks 341 References Luminescence of Supramolecular Gold-Containing Materials 347 José María López-de-Luzuriaga 6.1 Introduction. Conditions for Luminescence in Gold Complexes Luminescent Supramolecular Gold Entities Networks from Mononuclear Units Networks from Dinuclear Units Networks from Trinuclear Units Networks from Higher Nuclearity Systems Luminescent Supramolecular Gold Heterometal Entities Supramolecular Gold Group 11 Metal Complexes Other Supramolecular Gold Heterometal Complexes Concluding Remarks 398 References Liquid Crystals 403 Manuel Bardají 7.1 Introduction What Are Liquid Crystals? What Are Metallomesogens? Liquid Crystals Characterization Liquid Crystals Applications The Advantages of Gold Gold Mesogens Alkynyl Ligands Azobenzene Ligands Carbene Ligands Dithiobenzoate Ligands Isocyanide Ligands Combined with an Alkynyl Ligand Combined with Halides or Pseudohalides Combined with a Perhaloaryl Ligand Cationic bis(isocyanide) Compounds Chiral Isocyanide Binary Mixtures of Isocyanide Derivatives Perhaloaryl Ligands Pyrazolate Ligands Stilbazol Ligands Concluding Remarks 426 References 426

5 IX 8 Catalysis 429 M. Carmen Blanco Ortiz 8.1 Introduction Transition Metal Catalysis Gold Catalysis Homogeneous Catalysis Nucleophilic Additions to C C Multiple Bonds Allenes as Substrates Alkenes as Substrates Alkynes as Substrates Enynes as Substrates Activation of Carbonyl Groups and Alcohols Hydrogenation Reactions Heterogeneous Catalysis Hydrogenation Reactions Alkenes Hydrogenation Hydrogenation of a,b-unsaturated Aldehydes Oxidation Reactions C H Bond Activation Oxidation of Alcohols and Aldehydes Epoxidation Direct Synthesis of Hydrogen Peroxide Reactions Involving Carbon Monoxide Carbon Monoxide Oxidation Water Gas Shift Reaction Concluding Remarks 482 References Concluding Remarks 491 M. Concepción Gimeno and Antonio Laguna References 494 Index 495

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