Modern Surface Organometallic Chemistry

  • ID: 2179826
  • Book
  • 725 Pages
  • John Wiley and Sons Ltd
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The first book on this hot topic represents an advanced overview of the field, covering everything from the basics to recent applications. Edited by internationally acclaimed experts respected throughout the community, the book is clearly divided into two sections.

The first part deals with the fundamentals, such as characterization techniques, metal clusters analogies, molecular modeling, and the emergence of solid supports, while the second part focuses on the applications in catalysis, organometallic syntheses, and in hybrid materials.

Backed by numerous examples from the recent literature, this is a key reference for organic, surface, catalytic and complex chemists, as well as those working with/on organometallics.
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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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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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