Fundamentals of Organometallic Catalysis

  • ID: 2293082
  • Book
  • 472 Pages
  • John Wiley and Sons Ltd
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Catalysis, the basic principle for overcoming the kinetic inhibition of chemical reactions, is fundamental in chemistry. In particular, organometallic catalysis plays an overwhelming role in both research and industry. It opens the way to entirely novel synthetic methods and finds widespread applications ranging from mass–production of everyday polymers to stereocontrolled synthesis of bioactive chemicals used as pharmaceuticals and agrochemicals. The targeted development of improved and novel catalysts demands understanding of the relationships between their structures and catalytic properties. Accordingly, this textbook offers the reader a fundamental understanding of the course of organometallic–catalyzed reactions, starting at the molecular level. The initial chapters explain the principles of catalysis and the elementary steps in organometallic catalysis. The book then explores important organometallic–catalyzed reactions, with a focus on mechanism. Current developments are emphasized throughout. Asymmetric synthesis is covered in depth. Finally, the book examines the catalytic behavior of particular metalloenzymes. A look at nitrogen fixation offers a comparative examination of the three major areas of catalysis – homogeneous, heterogeneous, and enzymatic.

In addition to problems, the textbook offers solutions, making the book an invaluable learning tool. It is a must–have for advanced students in chemistry and biochemistry, as well as for inorganic and organic chemists, for those working with organometallics, and for those specializing in catalysis.
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Preface

INTRODUCTION

The Beginnings of Catalytic Research

The Catalysis Definitions of Berzelius and Ostwald

PRINCIPLES OF ORGANOMETALLIC CATALYSIS

Homogeneous versus Heterogeneous Catalysis

Catalytic Cycles

Activity and Productivity of Catalysts

Selectivity and Specificity of Catalysts

Determination of Catalytic Mechanisms

Glossary for Catalysis

The Development of Organometallic Catalysis

ELEMENTARY STEPS IN ORGANOMETALLIC CATALYSIS

Cleavage and Coordination of Ligands

Oxidative Addition and Reductive Elimination

Oxidative Coupling and Reductive Cleavage

Olefin Insertion and Beta–Hydrogen Elimination

Alpha–Hydrogen Elimination and Carbene Insertion Reactions

Addition of Nucleophiles and Heterolytic Fragmentation

Insertion and Extrusion of CO

One–Electron Reduction and Oxidation

HYDROGENATION OF OLEFINS

Introduction

The Wilkinson Catalyst

Enantioselective Hydrogenation

Dihydrogen Complexes and H2 Activation

Transfer Hydrogenation

HYDROFORMYLATION OF OLEFINS AND FISCHER–TROPSCH SYNTHESIS

Cobalt Catalysts

Phosphane–Modified Rhodium Catalysts

Enantioselective Hydroformylation

Significance of Hydroformylation and Outlook

The Fischer–Tropsch Synthesis

CARBONYLATION OF METHANOL AND WATER–GAS SHIFT REACTION

Principles

The Monsanto Process

Synthesis of Acetic Anhydride

The Cativa Process

Water–Gas Shift Reaction and Carbon Monoxide Dehydrogenases

METATHESIS

Metathesis of Olefins

Metathesis of Alkynes

Enyne Metathesis

Delta–Bond Metathesis

Metathesis of Alanes

OLIGOMERIZATION OF OLEFINS

Ziegler Growth Reaction

Nickel Effect and Nickel–Catalyzed Dimerization of Ethene

Trimerization of Ethene

Shell Higher Olefin and Alpha–Sablin Processes

POLYMERIZATION OF OLEFINS

Introduction

Ethene Polymerization

Propene Polymerization

Metallocene Catalysts

Nonmetallocene Catalysts

Copolymerization of Olefins and CO

C–C LINKAGE OF DIENES

Introduction

Allyl and Butadiene Complexes

Organometallic Elementary Steps of Allyl Ligands

Oligomerization and Telomerization of Butadiene

Polymerization of Butadiene

C–C COUPLING REACTIONS

Palladium–Catalyzed Cross–Coupling Reactions

The Heck Reaction

Palladium–Catalyzed Allylic Alkylation

HYDROCYANATION, HYDROSILYLATION, AND HYDROAMINATION OF OLEFINS

Introduction

Hydrocyanation

Hydrosilylation

Hydroamination

OXIDATION OF OLEFINS AND ALKANES

The Wacker Process

Epoxidation of Olefins

C–H Functionalization of Alkanes

NITROGEN FIXATION

Fundamentals

Heterogeneously Catalyzed Nitrogen Fixation

Enzyme–Catalyzed Nitrogen Fixation

Homogeneously Catalyzed Nitrogen Fixation

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Dirk Steinborn
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