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Homogeneous Catalysis Mechanisms and Industrial Applications

Homogeneous Catalysis Mechanisms and Industrial Applications

By Sumit Bhaduri, Doble Mukesh

The only up-to-date, concise textbook available for a short course in organometallic chemistry and homogeneous catalysis, Homogeneous Catalysis clearly explains the basic principles of organometallic chemistry, homogeneous catalysis, and relevant technological issues. Providing a balanced treatment of the recent breakthroughs and developments while also detailing earlier discoveries and the fundamentals of homogeneous catalysis,Homogeneous Catalysis Mechanisms and Industrial Applications provides problems and answers, along with real-life case studies, extensive references to cutting-edge research with application potential and leading patents, and examples from proven industrial processes with clear discussions on environmental and techno-commercial issues.

Editorial Reviews

Journal of Chemical Education

The writing style is one that students will like. It is clear, informal, and yet terse…this book could be used as the primary text for a course in catalysis…

SciTech Book News

A self-study guide for inorganic chemists seeking to know how to use the method, which has found application in the chemical, fine chemical, and pharmaceutical industries.

Booknews

A self-study guide for inorganic chemists seeking to know how to use the method, which has found application in the chemical, fine chemical, and pharmaceutical industries. Researchers with large Indian companies, Bhaduri (Northwestern U.) and Mukesh survey the literature up to March 1999 from a practical perspective to detail homogeneous catalytic reactions that have proven successful in industrial applications. They describe mechanistic principles, fundamental chemical and chemical engineering concepts, and example applications in selected industrial processes. Annotation c. Book News, Inc., Portland, OR (booknews.com)

From the Publisher

“The writing style is one that students will like. It is clear, informal, and yet terse…this book could be used as the primary text for a course in catalysis…” (Journal of Chemical Education, Vol. 78, No. 7, July 2001)

“A self-study guide for inorganic chemists seeking to know how to use the method, which has found application in the chemical, fine chemical, and pharmaceutical industries.” (SciTech Book News, Vol. 24, No. 4, December 2000)

Product Details

Table of Contents

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Preface xiii
1 Chemical Industry and Homogeneous Catalysis 1
1.1 Feed Stocks and Definitions 1
1.2 Feed Stock to Basic Building Blocks by Heterogeneous Catalysis 2
1.3 Basic Building Blocks to Downstream Products by Homogeneous Catalysis 4
1.4 Comparison Among Different Types of Catalysis 5
1.5 What Is To Follow–A Summary 8
Problems 10
Bibliography 11
2 Basic Chemical Concepts 13
2.1 The Metal 13
2.1.1 Oxidation State and Electron Count 13
2.1.2 Coordinative Unsaturation 15
2.1.3 Rare Earth Metals 17
2.2 Important Properties of Ligands 17
2.2.1 CO, R[subscript 2]C=CR[subscript 2], PR[subscript 3], and H[superscript -] as Ligands 17
2.2.2 Alkyl, Allyl, and Alkylidene Ligands 18
2.3 Important Reaction Types 19
2.3.1 Oxidative Addition and Reductive Elimination 19
2.3.2 Insertion Reactions 22
2.3.3 [beta]-Hydride Elimination 23
2.3.4 Nucleophilic Attack on a Coordinated Ligand 23
2.4 Energy Considerations–Thermodynamics and Kinetics 25
2.5 Catalytic Cycle and Intermediates 25
2.5.1 Kinetic Studies 28
2.5.2 Spectroscopic Studies 29
2.5.3 Model Compounds and Theoretical Calculations 30
Problems 33
Bibliography 35
3 Chemical Engineering Fundamentals 37
3.1 Reactor Design 37
3.1.1 Stirred Tank Reactors 39
3.1.2 Tubular Reactors 41
3.1.3 Membrane Reactors 42
3.1.4 Construction Materials 43
3.2 Operating Conditions 43
3.3 Mass Transfer in Multiphase Reactions 44
3.4 Heat Transfer 45
3.5 Catalyst Recovery 46
3.6 Unit Operations 47
3.6.1 Crystallization and Filtration 47
3.6.2 Distillation 47
3.6.3 Liquid-Liquid Extraction 49
3.6.4 Gas-Liquid Absorption (or Scrubbing) 50
3.7 Safety Aspects 50
3.8 Effluent and Waste Disposal 51
3.9 Economics 51
Problems 52
Bibliography 54
4 Carbonylation 55
4.1 Introduction 55
4.2 Manufacture of Acetic Acid 56
4.2.1 The Monsanto Process–The Catalytic Cycle 56
4.2.2 Mechanistic Studies and Model Compounds 59
4.2.3 The BASF Process–The Catalytic Cycle 60
4.2.4 BASF Process–Mechanistic Studies 61
4.3 Water-Gas Shift Reaction and Rhodium-Catalyzed Carbonylation 62
4.4 Fischer-Tropsch Reaction and Cobalt-Catalyzed Carbonylation 64
4.5 Rhodium-Catalyzed Carbonylation of Other Alcohols 66
4.6 Carbonylation of Methyl Acetate 68
4.6.1 Mechanism and Catalytic Cycle 69
4.7 Carbonylation of Alkynes; Manufacture of Methyl Methacrylate 70
4.7.1 Mechanism and Catalytic Cycle 71
4.8 Other Carbonylation and Hydrocarboxylation Reactions 74
4.9 Engineering Aspects 77
Problems 79
Bibliography 82
5 Hydroformylation 85
5.1 Background 85
5.2 The Rhodium Process 86
5.2.1 The Catalytic Cycle 86
5.2.2 Product Selectivity 88
5.2.3 Mechanistic Studies 88
5.2.4 The Phosphorus Ligands and Selectivity 90
5.2.5 Water-Soluble Phosphines and Rhodium Recovery 92
5.2.6 Catalyst and Ligand Degradation 95
5.3 Cobalt-Based Hydroformylation 96
5.4 Other Hydroformylation Reactions 98
5.5 Engineering Aspects 99
Problems 99
Bibliography 102
6 Polymerization 105
6.1 Introduction 105
6.1.1 Polyethylene 105
6.1.2 Polypropylene 106
6.2 Catalysts for Polyethylene 107
6.3 Catalysts for Polypropylene 108
6.4 Catalytic Cycle for Alkene Polymerization 109
6.4.1 Cossee-Arlman Mechanism 109
6.4.2 Mechanism of Alkene Insertion 111
6.4.3 Mechanistic Evidence 113
6.5 Metallocene Catalysts 113
6.5.1 Structures of Metallocene Catalysts and the Co-catalysts 114
6.5.2 Special Features and Advantages of Metallocene Catalysts 118
6.5.3 Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts 119
6.6 Chromocene and Heterogeneous Catalysts 123
6.7 Polymers of Other Alkenes 125
6.8 Engineering Aspects 125
Problems 127
Bibliography 130
7 Other Alkene-Based Homogeneous Catalytic Reactions 133
7.1 Introduction 133
7.2 Isomerization of Alkenes 133
7.2.1 Catalytic Cycle 134
7.3 Hydrogenation of Alkenes 135
7.3.1 Catalytic Cycle 136
7.3.2 Mechanistic Evidence 137
7.4 Oligomerization of Ethylene 138
7.4.1 Shell Higher Olefin Process 139
7.5 Di-, Tri-, and Codimerization Reactions 142
7.5.1 Dimerization of Propylene 142
7.5.2 Di- and Trimerization of Butadiene 142
7.5.3 Dimerization of Butadiene with Ethylene 147
7.6 Metathesis Reactions 147
7.6.1 Mechanistic Studies 147
7.7 Hydrocyanation 151
7.7.1 Catalysts for Hydrocyanation 153
7.7.2 Catalytic Cycle for the First Stage 154
7.7.3 Catalytic Cycle for the Second Stage 156
7.8 Hydrosilylation 159
7.8.1 Catalytic Cycle and Mechanism 160
7.9 C-C Coupling and Cyclopropanation Reactions 161
7.9.1 Catalytic Cycle for the Heck Reaction 163
7.9.2 Catalytic Cycle for Cyclopropanation 163
Problems 165
Bibliography 168
8 Oxidation 171
8.1 Introduction 171
8.2 Wacker Oxidation 172
8.2.1 The Background Chemistry 173
8.2.2 Catalytic Cycle and Mechanism 174
8.3 Metal-Catalyzed Liquid-Phase Autoxidation 176
8.3.1 Mechanism of Autoxidation 177
8.3.2 Special Features of Cyclohexane Oxidation 179
8.3.3 Special Features of p-Xylene Oxidation 181
8.4 Polymers (Polyesters and Polyamides) from Autoxidation Products 182
8.5 Epoxidation of Propylene 183
8.5.1 Catalytic Cycle and the Mechanism of Propylene Epoxidation 184
8.6 Oxo Complexes as Homogeneous Oxidation Catalysts 186
8.6.1 Mechanism of Oxidation by Oxo Compounds 187
8.7 Engineering and Safety Considerations 188
Problems 190
Bibliography 193
9 Asymmetric Catalysis 195
9.1 Introduction 195
9.2 General Features of Chiral Ligands and Complexes 196
9.3 Mechanisms and Catalytic Cycles 202
9.3.1 Mechanism of Asymmetric Hydrogenation 203
9.3.2 Asymmetric Isomerization and Mechanism 207
9.3.3 Asymmetric Epoxidation of Allylic Alcohols and Mechanisms 209
9.3.4 Asymmetric Epoxidation of Alkenes other than Allyl Alcohols 211
9.3.5 Asymmetric Hydrolysis of Epoxides 212
9.4 Asymmetric Dihydroxylation Reaction 215
9.4.1 Mechanism of ADH Reaction 216
9.5 Asymmetric Catalytic Reactions of C-C Bond Formation 217
9.5.1 Asymmetric Hydroformylation Reaction 218
9.5.2 Mechanism of Asymmetric Hydroformylation Reaction 221
9.5.3 Asymmetric Hydrocyanation Reaction 223
9.5.4 Nitroaldol Condensation 225
Problems 227
Bibliography
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