Homogeneous Catalysis : Mechanisms and

Problems of variable complexities accompanying each chapter.

SUMIT BHADURI, PhD, is a visiting professor at Northwestern University, Evanston, Illinois, and head of research for Reliance Industries Limited, Indias largest private sector company. <p> DOBLE MUKESH, PhD, is Senior Scientist with ICI India R & T Center, Thane, India.

Preface

xiii

Chemical Industry and Homogeneous Catalysis

1

(12)

Feed Stocks and Definitions

1

(1)

Feed Stock to Basic Building Blocks by Heterogeneous Catalysis

2

(2)

Basic Building Blocks to Downstream Products by Homogeneous Catalysis

4

(1)

Comparison Among Different Types of Catalysis

5

(3)

What Is To Follow---A Summary

8

(5)

Problems

10

(1)

Bibliography

11

(2)

Basic Chemical Concepts

13

(24)

The Metal

13

(4)

Oxidation State and Electron Count

13

(2)

Coordinative Unsaturation

15

(2)

Rare Earth Metals

17

(1)

Important Properties of Ligands

17

(2)

CO, R2C=CR2, PR3, and H- as Ligands

17

(1)

Alkyl, Allyl, and Alkylidene Ligands

18

(1)

Important Reaction Types

19

(6)

Oxidative Addition and Reductive Elimination

19

(3)

Insertion Reactions

22

(1)

β-Hydride Elimination

23

(1)

Nucleophilic Attack on a Coordinated Ligand

23

(2)

Energy Considerations---Thermodynamics and Kinetics

25

(1)

Catalytic Cycle and Intermediates

25

(12)

Kinetic Studies

28

(1)

Spectroscopic Studies

29

(1)

Model Compounds and Theoretical Calculations

30

(3)

Problems

33

(2)

Bibliography

35

(2)

Chemcal Engineering Fundamentals

37

(18)

Reactor Design

37

(6)

Stirred Tank Reactors

39

(2)

Tubular Reactors

41

(1)

Membrane Reactors

42

(1)

Construction Materials

43

(1)

Operating Conditions

43

(1)

Mass Transfer in Multiphase Reactions

44

(1)

Heat Transfer

45

(1)

Catalyst Recovery

46

(1)

Unit Operations

47

(3)

Crystallization and Filtration

47

(1)

Distillation

47

(2)

Liquid-Liquid Extraction

49

(1)

Gas--Liquid Absorption (or Scrubbing)

50

(1)

Safety Aspects

50

(1)

Effuent and Waste Disposal

51

(1)

Economics

51

(4)

Problems

52

(2)

Bibliography

54

(1)

Carbonylation

55

(30)

Introduction

55

(1)

Manufacture of Acetic Acid

56

(6)

The Monsanto Process---The Catalytic Cycle

56

(3)

Mechanistic Studies and Model Compounds

59

(1)

The BASF Process---The Catalytic Cycle

60

(1)

BASF Process---Mechanistic Studies

61

(1)

Water-Gas Shift Reaction and Rhodium-Catalyzed Carbonylation

62

(2)

Fischer-Tropsch Reaction and Cobalt-Catalyzed Carbonylation

64

(2)

Rhodium-Catalyzed Carbonylation of Other Alcohols

66

(2)

Carbonylation of Methyl Acetate

68

(2)

Mechanism and Catalytic Cycle

69

(1)

Carbonylation of Alkynes; Manufacture of Methyl Methacrylate

70

(4)

Mechanism and Catalytic Cycle

71

(3)

Other Carbonylation and Hydrocarboxylation Reactions

74

(3)

Engineering Aspects

77

(8)

Problems

79

(3)

Bibliography

82

(3)

Hydroformylation

85

(20)

Background

85

(1)

The Rhodium Process

86

(10)

The Catalytic Cycle

86

(2)

Product Selectivity

88

(1)

Mechanistic Studies

88

(2)

The Phosphorus Ligands and Selectivity

90

(2)

Water-Soluble Phosphines and Rhodium Recovery

92

(3)

Catalyst and Ligand Degradation

95

(1)

Cobalt-Based Hydroformylation

96

(2)

Other Hydroformylation Reactions

98

(1)

Engineering Aspects

99

(6)

Problems

99

(3)

Bibliography

102

(3)

Polymerization

105

(28)

Introduction

105

(2)

Polyethylene

105

(1)

Polypropylene

106

(1)

Catalysts for Polyethlene

107

(1)

Catalysts for Polypropylene

108

(1)

Catalytic Cycle for Alkene Polymerization

109

(4)

Cossee--Arlman Mechanism

109

(2)

Mechanism of Alkene Insertion

111

(2)

Mechanistic Evidence

113

(1)

Metallocene Catalysts

113

(10)

Structures of Metallocene Catalysts and the Co-catalysts

114

(4)

Special Features and Advantages of Metallocene Catalysts

118

(1)

Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts

119

(4)

Chromocene and Heterogeneous Catalysts

123

(2)

Polymers of Other Alkenes

125

(1)

Engineering Aspects

125

(8)

Problems

127

(3)

Bibliography

130

(3)

Other Alkene-Based Homogeneous Catalytic Reactions

133

(38)

Introduction

133

(1)

Isomerization of Alkenes

133

(2)

Catalytic Cycle

134

(1)

Hydrogenation of Alkenes

135

(3)

Catalytic Cycle

136

(1)

Mechanistic Evidence

137

(1)

Oligomerization of Ethylene

138

(4)

Shell Higher Olefin Process

139

(3)

Di-, Tri-, and Codimerization Reactions

142

(5)

Dimerization of Propylene

142

(1)

Di- and Trimerization of Butadiene

142

(5)

Dimerization of Butadiene with Ethylene

147

(1)

Metathesis Reactions

147

(4)

Mechanistic Studies

147

(4)

Hydrocyanation

151

(8)

Catalysts for Hydrocyanation

153

(1)

Catalytic Cycle for the First Stage

154

(2)

Catalytic Cycle for the Second Stage

156

(3)

Hydrosilylation

159

(2)

Catalytic Cycle and Mechanism

160

(1)

C--C Coupling and Cyclopropanation Reactions

161

(10)

Catalytic Cycle for the Heck Reaction

163

(1)

Catalytic Cycle for Cyclopropanation

163

(2)

Problems

165

(3)

Bibliography

168

(3)

Oxdation

171

(24)

Introduction

171

(1)

Wacker Oxidation

172

(4)

The Background Chemistry

173

(1)

Catalytic Cycle and Mechanism

174

(2)

Metal-Catalyzed Liquid-Phase Autoxidation

176

(6)

Mechanism of Autoxidation

177

(2)

Special Features of Cyclohexane Oxidation

179

(2)

Special Features of p-Xylene Oxidation

181

(1)

Polymers (Polyesters and Polyamides) from Autoxidation Products

182

(1)

Epoxidation of Propylene

183

(3)

Catalytic Cycle and the Mechanism of Propylene Epoxidation

184

(2)

Oxo Complexes as Homogeneous Oxidation Catalysts

186

(2)

Mechanism of Oxidation by Oxo Compounds

187

(1)

Engineering and Safety Considerations

188

(7)

Problems

190

(3)

Bibliography

193

(2)

Asymmetric Catalysis

195

(38)

Introduction

195

(1)

General Features of Chiral Ligands and Complexes

196

(6)

Mechanisms and Catalytic Cycles

202

(13)

Mechanism of Asymmetric Hydrogenation

203

(4)

Asymmetric Isomerization and Mechanism

207

(2)

Asymmetric Epoxidation of Allylic Alcohols and Mechanisms

209

(2)

Asymmetric Epoxidation of Alkenes other than Allyl Alcohols

211

(1)

Asymmetric Hydrolysis of Epoxides

212

(3)

Asymmetric Dihydroxylation Reaction

215

(2)

Mechanism of ADH Reaction

216

(1)

Asymmetric Catalytic Reactions of C--C Bond Formation

217

(16)

Asymmetric Hydroformylation Reaction

218

(3)

Mechanism of Asymmetric Hydroformylation Reaction

221

(2)

Asymmetric Hydrocyanation Reaction

223

(2)

Nitroaldol Condensation

225

(2)

Problems

227

(4)

Bibliography

231

(2)

Index

233

What is included with this book?

The New copy of this book will include any supplemental materials advertised. Please check the title of the book to determine if it should include any access cards, study guides, lab manuals, CDs, etc.

The Used, Rental and eBook copies of this book are not guaranteed to include any supplemental materials. Typically, only the book itself is included. This is true even if the title states it includes any access cards, study guides, lab manuals, CDs, etc.

FREE SHIPPING

Rent More, Save More! Use code: BBRENTAL

5% off 1 book, 7% off 2 books, 10% off 3+ books

Homogeneous Catalysis : Mechanisms and Industrial Applications

Summary

Author Biography

Table of Contents

Supplemental Materials

FREE SHIPPING

Rent More, Save More! Use code: BBRENTAL

5% off 1 book, 7% off 2 books, 10% off 3+ books

Homogeneous Catalysis : Mechanisms and Industrial Applications

Summary

Author Biography

Table of Contents

Supplemental Materials

Digital License