Modern Surface Organometallic Chemistry

Jean Marie Basset is Research Director at CNRS and Director of the Laboratory of Surface Organometallic Chemistry at CPE in Lyon. He received many awards including the grand prix (Prix Süe-1997) of the French Chemical society, the Max Planck Award in Germany, and the IFP Award of the French Academy of Sciences (1998). He is the author of 472 publications, 45 patents and is a member of the French Academy of Sciences and of the French Academy of Technologies as well of the Europan Academy of Sciences. His research interests are mostly centered in the field of Surface Organometallic Chemistry.Rinaldo Psaro is Director of the CNR Institute of Molecular Science and Technologies, Milano Italy. The general scientific interest is the development of new methods for the preparation of more efficient and eco-compatible catalytic systems for fine chemicals and commodities, to achieve higher performances, simpler preparation methods, conditions allowing for extended recycling. Author or co-author of 3 international patents and 162 papers on international journals on the field of surface organometallic chemistry, catalyst characterisation and heterogeneous catalysis.Dominique Roberto is Full Professor of General and Inorganic Chemistry at the Milan University. Author of 81 publications on highly qualified journals, her current research interests cover molecular engineering and nanoorganization of coordination and organometallic compounds with luminescent or non-linear optical properties, coordination complexes for solar cell application, and surface organometallic chemistry. For her research, she received the "Flavio Bonati" (1996) and the "Federchimica-per un futuro intelligente" (1998) awards.Renato Ugo is Full Professor of Inorganic Chemistry at Milan University. He received many awards including the Gold medal of the President of the Italian Republic for advancement in science (2000) and the Pino medal (2006). President of the Italian Association of Industrial Research, he is a member of the "Accademia Nazionale dei Lincei". He is author of ca 250 publications on highly qualified journals in the field of coordination chemistry, catalysis, surface organometallic chemistry, and recently nonlinear optics.

Covering everything from the basics to recent applications, this monograph represents an advanced overview of the field. Edited by internationally acclaimed experts respected throughout the community, the book is clearly divided into sections on fundamental and applied surface organometallic chemistry. Backed by numerous examples from the recent literature, this is a key reference for all chemists.

Covering everything from the basics to recent applications, this monograph represents an advanced overview of the field. Edited by internationally acclaimed experts respected throughout the community, the book is clearly divided into sections on fundamental and applied surface organometallic chemistry.

PrefaceON THE ORIGINS AND DEVELOPMENT OF ?SURFACE ORGANOMETALLIC CHEMISTRY?The Basic ConceptUse of Probe Molecules on Metallic Surfaces as Evidence of Coordination and Organometallic Chemistry at Metal SurfacesChemical and Structural Analogy between Molecular Clusters and Small Metallic ParticlesAnalogy between Supported Molecular Clusters and Small Supported Catalytic ParticlesFoundation of Surface Organometallic ChemistryFrom Organometallic Surface Chemistry to the Elementary Steps Occurring on Surfaces and Stabilization by the Surface of Rather Unstable Molecular SpeciesFrom Surface Organometallic Chemistry on Oxides to Surface Organometallic Chemistry on MetalsFrom Surface Organometallic Chemistry to Surface-Mediated Organometallic SynthesisSingle Metal Site Heterogeneous Catalysts and the Design of New CatalystsPREPARATION OF SINGLE SITE CATALYSTS ON OXIDES AND METALS PREPARED VIA SURFACE ORGANOMETALLIC CHEMISTRYIntroductionSurface Organometallic Chemistry on OxidesReaction of Organometallic Compounds with Supported or Unsupported Group VIII Metals ParticlesConclusionCATALYTIC PROPERTIES OF SINGLE SITE CATALYSTS PREPARED VIA SURFACE ORGANOMETALIC CHEMISTRY ON OXIDES AND ON METALSIntroductionStoichiometric Activation of Alkane C-H BondsAlkane C-C Bond Activation by Tantalum Hydrides. Low Temperature Catalytic Hydrogenolysis of AlkanesMetathesis of Acyclic AlkanesCross-Metathesis Reactions of AlkanesHomologation of AlkanesPolystyrene Modification and Hydrogenolysis of Linear Alkanes and Polyethylene by a Supported Zirconium HydrideOlefin MetathesisOlefin EpoxidationDeperoxidation of Cyclohexyl HydroperoxideSome Applications of Supported Nanoparticles Modified by OrganometallicsConclusionBUILDING BLOCK APPROACHES TO NANOSTRUCTURED, SINGLE SITE, HETEROGENEOUS CATALYSTSIntroductionCurrent Challenges in CatalysisWhat is a Nanostructured Catalyst?Benefits of Nanostructuring CatalystsCurrent Approaches to Nanostructured CatalystsBuilding Block Approaches to Nanostructured Materials and CatalysisNanostructured Catalysts via a Non-Aqueous Building Block MethodologyA Model for the Growth of Building Block Matrices and a Nanostructuring StrategyA General Procedure for Preparing Nanostructured Catalysts in Silicate MatricesAtomically Dispersed Titanium and Vanadium, Single Site CatalystsBridge between Nanostructuring and CatalysisSummaryTRANSITION METAL SINGLE SITE CATALYSTS ? FROM HOMOGENEOUS TO IMMOBILIZED SYSTEMSIntroductionCovalently Anchored Organometallic Complexes on Unmodified SilicaAnchoring of Organometallic Complexes via the Metal CenterOrganometallic Complexes Anchored via a Covalent Linkage to a LigandNoncovalently Anchored Organometallic ComplexesEncapsulated Organometallic ComplexesConclusionsCONTROLLED PREPARATION OF HETEROGENEOUS CATALYSTS FOR CHEMO- AND ENANTIOSELECTIVE HYDROGENATION REACTIONSIntroductionCatalyst Preparation and CharacterizationHydrogenation of Alpha,Beta-Unsaturated AldehydesHydrogenation of Aromatic KetonesEnantioselective Hydrogenation ReactionsConclusionsWELL-DEFINED SURFACE RHODIUM SILOXIDE COMPLEXES AND THEIR APPLICATION TO CATALYSISMolecular versus Immobilized Transition Metal Siloxide Complexes in CatalysisSynthesis, Characterization and Catalytic Activity of Well-Defined Surface Rhodium Siloxide ComplexesSolid-State NMR Method in Catalysis by Surface OrganometallicsMechanism of Hydrosilylation Catalyzed by Surface versus Soluble Rhodium Siloxide ComplexesCARBONYL COMPOUNDS AS METALLIC PRECURSORS OF TAILORED SUPPORTED CATALYSTSIntroductionCatalysts Prepared from Metal Carbonyls of Groups 6, 7, 10 and GoldCatalysts Prepared from Metal Carbonyls of Group 8: Iron, Ruthenium and OsmiumCatalysts Prepared from Metal Carbonyls of Group 9: Cobalt, Rhodium and IridiumConcluding RemarksEXPLOITING SURFACE CHEMISTRY TO PREPARE METAL-SUPPORTED CATALYSTS BY ORGANOMETALLIC CHEMICAL VAPOR DEPOSITIONIntroductionSurface Organometallic ChemistryStrategies to Avoid the Contamination of Metal DepositsHow to Manage the Nucleation and Growth StepsConcluding RemarksADVANCED DESIGN OF CATALYST SURFACES WITH METAL COMPLEXES FOR SELECTIVE CATALYSISIntroductionIsolation and Epoxidation Activity of a Coordinatively Unsaturated Ru Complex at a SiO2 SurfaceChiral Self-Dimerization of V Complexes on a SiO2 Surface for Asymmetric CatalysisMolecular Imprinting Rh-Dimer and Rh-Monomer CatalystsRe Clusters in HZSM-5 Pores for Direct Phenol SynthesisConclusionSURFACE ORGANOMETALLIC CHEMSITRY OF D(0) METAL COMPLEXESIntroductionLigands Susceptible to React with Hydroxyl Groups of an Inorganic OxideLigands Susceptible to Reaction with Lewis Acid Sites of Inorganic OxidesReactivity of Hydrocarbyl-Metal Complexes and the Metal AtomInorganic Oxides as Supports for Organometallic SpeciesModels for Surface Organometallic SpeciesTuning the Catalytic Activity of Surface Organometallic SpeciesRelevant Aspects of the Full Characterization of Some Selected SpeciesConcluding RemarksSURFACE ORGANOLANTHANIDE AND ?ACTINIDE CHEMISTRYIntroductionSurface Organolanthanide Chemistry SOLnCSurface Organoactinide Chemistry, SOAnCCatalytic Applications of SOLnC and SOAnCConclusions and PerspectivesISOCYANIDE BINDING MODES ON METAL SURFACES AND IN METAL COMPLEXESIntroductionModes of Isocyanide Coordination in Transition Metal ComplexesAdsorption of Isocyanides (C=N-R) on Metal SurfacesConclusionsMOLECULAR INSIGHT FOR SILICA-SUPPORTED ORGANOMETALLIC CHEMISTRY THROUGH TRANSITION METAL SILESQUIOXANESIntroductionOrganometallic POSS DerivativesConclusionsSURFACE-MEDIATED NANOSCALE FABRICATION OF METAL PARTICLES AND WIRES USING MESOPOROUS SILICA TEMPLATES AND THEIR SHAPE/SIZE DEPENDENCY IN CATALYSISIntroductionSurface-Mediated Synthesis of Metal/Alloy Nanowires Using Mesoporous TemplatesCharacterization of Nanowires and Nanoparticles in FSM-16 and HMM-1Mechanism for Formation of Pt Nanowires in Mesoporous Silica TemplatesIsolation and Characterization of Metal/Alloy Nanowires Free from the Silica SupportsNovel Surface-Mediated Fabrication of Rh and RhPt Nanoparticles Using Mesoporous Templates in Supercritical Carbon DioxideOther Surface-Mediated Synthesis of Metal Nanowires on Porous Membrane and Graphite StepsShape/Size Dependency in Catalysis of Metal/Alloy Nanowires and Particles in Mesoporous Silica TemplatesSynthesis of Pt and Au Nanoparticle Arrays in Mesoporous Silica Films and their Electric/Magnetic Properties in Terms of the Quantum-Size EffectConclusionSURFACE-MEDIATED ORGANOMETALLIC SYNTHESESIntroductionGroup 7: RheniumGroup 8Group 9Group 10Conclusion