One-stop reference on homogeneous catalysis, from general concepts through detailed examples and industrial applications

Accessible and richly illustrated, Applied Homogeneous Catalysis provides a concise overview of the broad field of homogeneous transition metal catalysis and its applications in the chemical industry. This newly revised and updated second edition puts special emphasis on green chemistry, sustainable resources, and processes.

The book is divided into five parts. Part I presents the basics of transition metal catalysis. Part II focuses on process engineering aspects. Part III provides details of the most important catalytic reactions. Part IV describes catalytic conversions closely related to classical homogeneous transition metal catalysis, such as nano-, electro-, photo- and organocatalysis. Part V covers new feedstocks and other topics, concluding with an outlook on future challenges of homogeneous catalysis.

The book contains numerous mechanistic details, technical information, and illustrative examples. The chapters are enlivened by various excursions that relate the content to everyday life or introduce important personalities. Didactically, the book is completed with learning objectives and take-home messages for each chapter, as well as more than 400 questions and answers for self-testing.

Written by a team of internationally renowned experts in the field, with a wealth of experience in industry and teaching, Applied Homogeneous Catalysis includes information on:

• Economic importance of industrial homogeneously-catalyzed reactions and basics of organometallic chemistry, including types of bonds, elemental steps, and mechanisms
• Common approaches for separating the homogeneous catalyst from the products after the reaction and using combinatorial chemistry and high throughput screening to achieve optimal results
• Activating "inactive" molecules such as carbon dioxide and nitrogen, and harnessing homogeneous catalysis for feedstock diversification by recycling polymers or using renewables.

Providing expansive coverage of the subject, Applied Homogeneous Catalysis is an essential guide for researchers and professionals in the pharmaceutical, polymer, and fine and bulk chemicals industries working on catalysis or entering the field, as well as for Master's and PhD students in organic chemistry, chemical engineering, and related fields.

Preface of the Authors xvii

0 Introduction: Adhering to the 12 Principles of Green Chemistry: How Does Homogeneous Catalysis Contribute? 1

Part I Chemical Basics 13

1 Definition, Variants and Examples: What Actually Is Catalysis? 15

1.1 Definition of Catalysis 15

1.2 The Different Varieties of Catalysis 18

1.3 The Directing Effect of the Catalyst 20

1.4 Sources of Information About Catalysis 21

2 A Brief History: Homogeneous Transition Metal Catalysis: A Young Science 25

2.1 Phase I: Inorganic Basic Chemicals (1898-1918) 26

2.2 Phase II: Refinery Processes: Syngas and Ethyne Chemistry (1919-1945) 27

2.3 Phase III: Petrochemical Industrial Products (1946-1970) 27

2.4 Phase IV: Fine Chemicals and Speciality Products (1971 to Date) 29

3 Industrial Homogeneous Catalysis: What Is the Economic Importance? 33

3.1 Application Areas of Catalysis 33

3.2 Important Homogeneous Catalysed Processes 33

3.3 Synthesis of Fine and Speciality Chemicals by Homogeneous Catalysis 34

3.4 Atom Economy and Environmental Factor 35

4 Definition of Important Terms: X, Y, S, STY, TON, TOF and more... 41

4.1 Conversion 42

4.2 Yield 43

4.3 Selectivity 44

4.3.1 Chemoselectivity 44

4.3.2 Regioselectivity 44

4.3.3 Diastereoselectivity 45

4.3.4 Enantioselectivity 45

4.4 Turnover Frequency 45

4.5 Turnover Number 46

4.6 Catalyst Lifetime 47

4.7 Space-Time-Yield 47

4.8 Catalyst Losses 48

4.9 Catalyst Stability/Deactivation and Recycling 49

4.10 Product Purity 49

4.11 Further Important Terms 51

4.12 The Choice Is Yours! 51

5 Basics of Organometallic Chemistry: Bonds, Elementary Steps and Mechanisms 55

5.1 Metal-Ligand Bonds 55

5.2 Change of Oxidation State (OS) 58

5.3 Change of Coordination Number (CN) and Coordination Geometry 58

5.4 The Elementary Steps 59

5.5 Catalytic Cycles 63

6 Transition Metal Compounds: The 'Captains' of Homogeneous Catalysis 67

6.1 Group 3 and Lanthanides 67

6.2 Metals of Group 4 67

6.3 MetalsofGroups5- 7 67

6.4 The 'Iron Metals' of Groups 8-10 68

6.5 The Noble Metals from Groups 8 to 10 70

6.6 Gold: A Noble Metal of Group 11 74

6.7 The Costs of Catalyst Metals 74

6.8 The Availability of Transition Metal Compounds 76

7 Ligands: The 'Helmsmen' of Homogeneous Catalysis 79

7.1 Steric Effects and Tolman's Ligand Cone Angle 80

7.2 Ligand's Electronic Effects 86

7.3 Chelating Ligands and Ligand Bite Angle 90

7.4 Hemilabile Ligands 95

7.5 Nitrogen-Based Ligands 95

7.6 Pincer Ligands 96

7.7 Ligand Syntheses 97

7.8 Ligand Stability and Decomposition 102

7.9 Costs and Accessibility of Ligands 104

8 Solvents in Homogeneous Catalysis: The Reaction Medium 107

8.1 General Aspects of Solvents 107

8.2 Physical Properties of Solvents - Solvent Parameters 108

8.3 Influence of Solvents on Homogeneous Catalysts 115

8.4 Solvent Availability and Costs 118

8.5 Solvent Purity 119

8.6 Solvent Selection Guides 120

8.7 Advanced Reaction Media for Homogeneous Catalysis 121

9 Enantioselective Catalysis: The "Special Case" 133

9.1 A Glossary of Asymmetric Catalysis 133

9.2 A Quick Look Back 136

9.3 The Mechanism of Asymmetric Catalytic Hydrogenation 139

9.4 Chiral Ligands 142

9.5 Overview of Homogeneously Catalysed Asymmetric Syntheses 143

9.6 Industrial Applications 143

10 Thermodynamics of Homogeneous Catalysis: When Does a Chemical Reaction Run? 147

10.1 Gibbs Energy and Energy Plot 147

10.2 Calculation or Assessment of the Free Reaction Enthalpy 149