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Modern Surface Organometallic Chemistry

Jean -Marie Basset (Editor), Rinaldo Psaro (Editor), Dominique Roberto (Editor), Renato Ugo (Editor)
ISBN: 978-3-527-31972-5
725 pages
August 2009
Modern Surface Organometallic Chemistry (3527319727) cover image
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.
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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

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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.
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This comprehensive book is edited by four eminent scientists, two of whom have helped pioneer the research area. Fifty investigators have contributed to the impressive array of 16 chapters, the breadth and depth of which render an encyclopedic flavor to the volume. (JACS, January 2010)

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