Modern Surface Organometallic Chemistry (2009)

Preface ON THE ORIGINS AND DEVELOPMENT OF ?SURFACE ORGANOMETALLIC CHEMISTRY? The Basic Concept Use of Probe Molecules on Metallic Surfaces as Evidence of Coordination and Organometallic Chemistry at Metal Surfaces Chemical and Structural Analogy between Molecular Clusters and Small Metallic Particles Analogy between Supported Molecular Clusters and Small Supported Catalytic Particles Foundation of Surface Organometallic Chemistry From Organometallic Surface Chemistry to the Elementary Steps Occurring on Surfaces and Stabilization by the Surface of Rather Unstable Molecular Species From Surface Organometallic Chemistry on Oxides to Surface Organometallic Chemistry on Metals From Surface Organometallic Chemistry to Surface-Mediated Organometallic Synthesis Single Metal Site Heterogeneous Catalysts and the Design of New Catalysts PREPARATION OF SINGLE SITE CATALYSTS ON OXIDES AND METALS PREPARED VIA SURFACE ORGANOMETALLIC CHEMISTRY Introduction Surface Organometallic Chemistry on Oxides Reaction of Organometallic Compounds with Supported or Unsupported Group VIII Metals Particles Conclusion CATALYTIC PROPERTIES OF SINGLE SITE CATALYSTS PREPARED VIA SURFACE ORGANOMETALIC CHEMISTRY ON OXIDES AND ON METALS Introduction Stoichiometric Activation of Alkane C-H Bonds Alkane C-C Bond Activation by Tantalum Hydrides. Low Temperature Catalytic Hydrogenolysis of Alkanes Metathesis of Acyclic Alkanes Cross-Metathesis Reactions of Alkanes Homologation of Alkanes Polystyrene Modification and Hydrogenolysis of Linear Alkanes and Polyethylene by a Supported Zirconium Hydride Olefin Metathesis Olefin Epoxidation Deperoxidation of Cyclohexyl Hydroperoxide Some Applications of Supported Nanoparticles Modified by Organometallics Conclusion BUILDING BLOCK APPROACHES TO NANOSTRUCTURED, SINGLE SITE, HETEROGENEOUS CATALYSTS Introduction Current Challenges in Catalysis What is a Nanostructured Catalyst? Benefits of Nanostructuring Catalysts Current Approaches to Nanostructured Catalysts Building Block Approaches to Nanostructured Materials and Catalysis Nanostructured Catalysts via a Non-Aqueous Building Block Methodology A Model for the Growth of Building Block Matrices and a Nanostructuring Strategy A General Procedure for Preparing Nanostructured Catalysts in Silicate Matrices Atomically Dispersed Titanium and Vanadium, Single Site Catalysts Bridge between Nanostructuring and Catalysis Summary TRANSITION METAL SINGLE SITE CATALYSTS ? FROM HOMOGENEOUS TO IMMOBILIZED SYSTEMS Introduction Covalently Anchored Organometallic Complexes on Unmodified Silica Anchoring of Organometallic Complexes via the Metal Center Organometallic Complexes Anchored via a Covalent Linkage to a Ligand Noncovalently Anchored Organometallic Complexes Encapsulated Organometallic Complexes Conclusions CONTROLLED PREPARATION OF HETEROGENEOUS CATALYSTS FOR CHEMO- AND ENANTIOSELECTIVE HYDROGENATION REACTIONS Introduction Catalyst Preparation and Characterization Hydrogenation of Alpha,Beta-Unsaturated Aldehydes Hydrogenation of Aromatic Ketones Enantioselective Hydrogenation Reactions Conclusions WELL-DEFINED SURFACE RHODIUM SILOXIDE COMPLEXES AND THEIR APPLICATION TO CATALYSIS Molecular versus Immobilized Transition Metal Siloxide Complexes in Catalysis Synthesis, Characterization and Catalytic Activity of Well-Defined Surface Rhodium Siloxide Complexes Solid-State NMR Method in Catalysis by Surface Organometallics Mechanism of Hydrosilylation Catalyzed by Surface versus Soluble Rhodium Siloxide Complexes CARBONYL COMPOUNDS AS METALLIC PRECURSORS OF TAILORED SUPPORTED CATALYSTS Introduction Catalysts Prepared from Metal Carbonyls of Groups 6, 7, 10 and Gold Catalysts Prepared from Metal Carbonyls of Group 8: Iron, Ruthenium and Osmium Catalysts Prepared from Metal Carbonyls of Group 9: Cobalt, Rhodium and Iridium Concluding Remarks EXPLOITING SURFACE CHEMISTRY TO PREPARE METAL-SUPPORTED CATALYSTS BY ORGANOMETALLIC CHEMICAL VAPOR DEPOSITION Introduction Surface Organometallic Chemistry Strategies to Avoid the Contamination of Metal Deposits How to Manage the Nucleation and Growth Steps Concluding Remarks ADVANCED DESIGN OF CATALYST SURFACES WITH METAL COMPLEXES FOR SELECTIVE CATALYSIS Introduction Isolation and Epoxidation Activity of a Coordinatively Unsaturated Ru Complex at a SiO2 Surface Chiral Self-Dimerization of V Complexes on a SiO2 Surface for Asymmetric Catalysis Molecular Imprinting Rh-Dimer and Rh-Monomer Catalysts Re Clusters in HZSM-5 Pores for Direct Phenol Synthesis Conclusion SURFACE ORGANOMETALLIC CHEMSITRY OF D(0) METAL COMPLEXES Introduction Ligands Susceptible to React with Hydroxyl Groups of an Inorganic Oxide Ligands Susceptible to Reaction with Lewis Acid Sites of Inorganic Oxides Reactivity of Hydrocarbyl-Metal Complexes and the Metal Atom Inorganic Oxides as Supports for Organometallic Species Models for Surface Organometallic Species Tuning the Catalytic Activity of Surface Organometallic Species Relevant Aspects of the Full Characterization of Some Selected Species Concluding Remarks SURFACE ORGANOLANTHANIDE AND ?ACTINIDE CHEMISTRY Introduction Surface Organolanthanide Chemistry SOLnC Surface Organoactinide Chemistry, SOAnC Catalytic Applications of SOLnC and SOAnC Conclusions and Perspectives ISOCYANIDE BINDING MODES ON METAL SURFACES AND IN METAL COMPLEXES Introduction Modes of Isocyanide Coordination in Transition Metal Complexes Adsorption of Isocyanides (C=N-R) on Metal Surfaces Conclusions MOLECULAR INSIGHT FOR SILICA-SUPPORTED ORGANOMETALLIC CHEMISTRY THROUGH TRANSITION METAL SILESQUIOXANES Introduction Organometallic POSS Derivatives Conclusions SURFACE-MEDIATED NANOSCALE FABRICATION OF METAL PARTICLES AND WIRES USING MESOPOROUS SILICA TEMPLATES AND THEIR SHAPE/SIZE DEPENDENCY IN CATALYSIS Introduction Surface-Mediated Synthesis of Metal/Alloy Nanowires Using Mesoporous Templates Characterization of Nanowires and Nanoparticles in FSM-16 and HMM-1 Mechanism for Formation of Pt Nanowires in Mesoporous Silica Templates Isolation and Characterization of Metal/Alloy Nanowires Free from the Silica Supports Novel Surface-Mediated Fabrication of Rh and RhPt Nanoparticles Using Mesoporous Templates in Supercritical Carbon Dioxide Other Surface-Mediated Synthesis of Metal Nanowires on Porous Membrane and Graphite Steps Shape/Size Dependency in Catalysis of Metal/Alloy Nanowires and Particles in Mesoporous Silica Templates Synthesis of Pt and Au Nanoparticle Arrays in Mesoporous Silica Films and their Electric/Magnetic Properties in Terms of the Quantum-Size Effect Conclusion SURFACE-MEDIATED ORGANOMETALLIC SYNTHESES Introduction Group 7: Rhenium Group 8 Group 9 Group 10 Conclusion