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Full Description
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.
Contents
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
10.3 Thermodynamic Analysis of Complex Reaction Systems 149
10.4 Advances in Computational Tools for Thermodynamics in Homogeneous Catalysis 151
11 Kinetics of Homogeneous Catalysis: How Does the Reaction Proceed? 159
11.1 Frequently Occurring Kinetics 159
11.2 The Use of Energy Profiles to Explain Selectivity 163
11.3 Execution of Experiments to Determine the Kinetics of a Reaction 164
11.4 A Concrete Example: Hydroformylation of Cyclooctene 165
11.5 Pitfalls in Kinetic Measurements 166
12 Overview of Spectroscopic Methods: Can We See into Homogeneous Catalysis? 169
12.1 UV/Visible Spectroscopy 170
12.2 IR Spectroscopy 171
12.3 Raman Spectroscopy 173
12.4 NMR Spectroscopy 174
12.5 Electrospray Ionisation Mass Spectroscopy (ESI-MS) 182
12.6 X-Ray Absorption Spectroscopy (XAS) and Extended X-ray absorption fine Structure Analysis (exafs) 184
12.7 Electron Paramagnetic Resonance Spectroscopy (EPR) 185
12.8 Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) 188
12.9 In situ, Operando and Combined Spectroscopy 189
Part II Process Engineering Fundamentals 193
13 Reactor Types: Where Homogeneous Catalysis Actually Occurs 195
13.1 Stirred Tank Reactor 195
13.2 Tubular Reactor 201
13.3 Transition variants between stirred tank reactor and plug flow reactor 202
13.4 Reactors for Gas/Liquid Reactions 203
13.5 Loop Reactors 205
13.6 Jet-Loop Reactor 205
13.7 Membrane Reactor 206
13.8 Microreactors 207
13.9 Special Reactors 208
13.10 The 'Agony of Choice' 208
14 Overview of Catalyst Separation Techniques: How Catalyst and Product Go Their Separate Ways After the Reaction 213
14.1 Separation Principles 213
14.2 Separation by Distillation 215
14.3 Separation by Precipitation 219
14.4 Separation by Crystallisation 221
14.5 Separation by Adsorption 222
14.6 Separation by Heterogenisation on a Solid Support 223
14.7 Separation by Membranes 223
14.8 Separation by Extraction 223
14.9 Separation of a Second Liquid Phase 225
15 Catalyst Separation by Membranes: A Barrier Between Products and Catalysts 229
15.1 Membranes 232
15.2 Key Figures 234
15.3 Technical Implementation 236
15.4 Industrial Applications 237
16 Immobilisation on Solid Supports: From Homogeneity to Heterogeneity 241
16.1 The Basic Principles 241
16.2 Solid-Phase Immobilisation 242
16.3 Supported-Liquid Phase (SLP) Immobilisation 246
16.4 Industrial Application 247
17 Liquid-Liquid Multiphase Systems: The Smart Approach to Catalyst Separation 249
17.1 Alteration of the Solubility of the Ligands by Selective Modifications 249
17.2 Variants of Multiphase Catalysis 251
18 Switchable Multiphase Systems: Triggering Separation of Homogeneous Mixtures 261
18.1 Temperature as a Switch 262
18.2 CO 2 Switchable Systems 270
18.3 Concluding Remarks to Recycling Methods 275
19 Optimisation Strategies: Combinatorial Synthesis, Design of Experiments and High-Throughput Screening 279
19.1 Combinatorial Chemistry 280
19.2 Design of Experiments (DoE) 283
19.3 High-Throughput Screening (HTS) 286
19.4 Virtual Screening (Computational Screening, Machine Learning) 299
20 Process Development in Miniplants: From Laboratory to Production 305
20.1 Combination of TMSs with Other Reactor Types 307
20.2 Improved Online Analytics 308
20.3 Application of TMSs for Complex Reactions in Continuous Operation 310
20.4 Combined Reaction Separation Processes 311
Part III Homogeneously Catalysed Reaction Types 315
21 An Overview of C--C-Bond Formation: A Guide Through the Jungle 319
22 Hydroformylation: The Industrial Route to Aldehydes and Alcohols 325
22.1 Main and Side Reactions 326
22.2 Catalysts 327
22.3 Mechanisms 331
22.4 Substrates 334
22.5 Asymmetric Hydroformylation 337
22.6 Syngas Surrogates 338
23 Carbonylation: The Versatile Insertions of Carbon Monoxide 341
23.1 Reactions Between CO and Hydrogen 341
23.2 Reactions of CO with Alkenes and Vinyl Arenes 343
23.3 Reactions of CO with Dienes 345
23.4 Reactions of CO with Alkynes 346
23.5 Reactions of CO with Alcohols 347
23.6 New Trends 348
24 Oligomerisation and Cyclooligomerisation: The Conversion of Unsaturated Aliphatics into Short Chains or Medium-Sized Rings 351
24.1 Oligomerisation of Alkenes 351
24.2 Dienes 359
24.3 Alkynes 361
24.4 Co-Oligomerisations 361
25 Metathesis: A 'Change-Your-Partners' Dance 365
25.1 The Many Variants of Alkene Metathesis 365
25.2 Mechanism and Catalysts 367
25.3 Industrial Applications 371
25.4 Other Types of Metatheses 373
25.5 Some Trends 375
26 Polymerisation: The Purposeful Assembly of Macromolecules 381
26.1 Polyethylene and Ziegler Catalysts 381
26.2 Polypropylene and Metallocene Catalysis 385
26.3 Further Polyalkenes and Copolymers 388
26.4 Polydienes 390
26.5 Polyketones 392
26.6 Polyalkynes 393
26.7 Post-Metallocenes 394
26.8 Some Trends 395
27 Telomerisation: The Construction of Functionalised Aliphatic Chains 397
27.1 Reactions, Mechanisms and Catalysts 397
27.2 Butadiene Telomerisation 399
27.3 Telomerisations with C 5 - and C 6 -Dienes 407
27.4 Terpenoic 1,3-Dienes 408
27.5 Enantioselective Telomerisations 408
27.6 Some Trends 409
28 Carbon-Carbon Coupling Reactions: Quite a lot of Name Reactions 413
28.1 Mizoroki-Heck Reactions 414
28.2 Sonogashira-Hagihara Reactions 417
28.3 Suzuki-Miyaura Reaction 419
28.4 Stille Coupling 422
28.5 Hiyama Coupling 423
28.6 Negishi Coupling 425
28.7 Kumada Coupling 426
29 Hydrogenation: C--H Bond Formation 429
29.1 Catalysts and Mechanisms 430
29.2 Asymmetric Hydrogenation 430
29.3 Hydrogenation of Various Functional Groups 432
29.4 Transfer Hydrogenations 436
29.5 Industrial Applications 437
29.6 Some Trends 440
30 Oxidation: C--O Bond Formation 443
30.1 Wacker Oxidation 443
30.2 Epoxidation 447
30.3 Asymmetric Dihydroxylation 451
30.4 Oxidative Cleavage of C=C Double Bonds 452
30.5 Oxidation of Cyclohexane 453
30.6 Oxidation of Alkyl Aromatics 454
30.7 Oxidation of Alcohols 456
30.8 Oxidation of Ketones (Baeyer-Villiger Oxidation) 457
31 Amination and Hydroamination: C--N Bond Formation 461
31.1 Amination of Aryl Halides 461
31.2 Hydroamination of Alkenes 464
31.3 Hydroaminations of 1,3-Dienes and Allenes 468
31.4 Hydroamination of Alkynes 470
31.5 Amination of Functional Groups 471
31.6 Aminohydroxylation 474
32 Hydrofunctionalisation: Formation of Further C--X Bonds 477
32.1 Hydrosilylation 477
32.2 Hydroboration 480
32.3 Hydration and Hydroalkoxylation 483
32.4 Hydrometalation 484
33 Isomerisation and Rearrangement: Migration of Double Bonds and Rearrangement of the Carbon Backbone 489
33.1 Isomerisation of Alkenes 489
33.2 Isomerisation of Alkenes with Functional Groups 492
33.3 Isomerisation of 1,3-Dienes, Allenes and Alkynes 496
33.4 Cyclic Compounds: Formation, Rearrangement and Splitting 497
Part IV Associated Catalysis 501
34 Tandem Reactions: Multiple Synthesis Steps in One Pot 503
34.1 General Taxonomy 503
34.2 Important Examples of Homogeneously Catalysed Tandem Reactions 508
35 Nanocatalysis: A Balancing Act Between Homogeneous and Heterogeneous Catalysis 519
35.1 Introduction 519
35.2 Synthesis and Properties of Nanocatalysts 521
35.3 Stabilisation of Nanoparticles 522
35.4 Heterogenisation of Nanoparticles on Solid Supports 525
35.5 Catalysis Involving Metal Nanoparticles 525
35.6 What Can Happen During a Reaction? 526
35.7 Homogeneous Catalysis or Nanocatalysis? 527
36 Electrocatalysis: Catalysis with Electrons 531
36.1 Water Splitting 533
36.2 Carbon Dioxide Reduction 534
36.3 Electrochemical In Situ Synthesis of Homogeneous Catalysts 535
36.4 Electrocatalytic Oxidations 535
37 Photocatalysis: Catalysis with Photons 537
38 Alternative Ways of Energy Input: Sono-, Microwave- and Mechanocatalysis 543
38.1 Sonocatalysis 543
38.2 Microwave Catalysis 546
38.3 Mechanocatalysis 551
39 Organocatalysis: Homogeneous Catalysis only with Organic Compounds 559
Part V New Resources 565
40 Alkane Activation: Acquisition of New Feedstocks 567
40.1 Mechanistic Considerations 568
40.2 c -O Formation via Alkane Oxidation 570
40.3 c -c-Linking Reactions 572
40.4 Hydrogen Migrations and C -C-Splitting Reactions 574
40.5 Further Alkane Functionalisations (C -X-Linkage Reactions) 576
41 Reactions with Carbon Dioxide: Activating an 'Inactive' Molecule 579
41.1 Carbon Dioxide and Alkanes 580
41.2 Carbon Dioxide and Alkenes 581
41.3 Carbon Dioxide and Dienes 584
41.4 Carbon Dioxide and Alkynes 588
41.5 Carbon Dioxide and Aromatic Compounds 590
41.6 Carbon Dioxide and Hydrogen (Reductions ofCO 2) 592
41.7 Carbon Dioxide and Epoxides 598
41.8 Carbon Dioxide and Amines 600
41.9 Carbon Dioxide-Containing Polymers 600
42 Nitrogen Activation: Reaching for the Air 605
42.1 Transition Metal-Nitrogen Complexes 607
42.2 Stoichiometric Reactions of the Nitrogen Molecule 609
42.3 Homogeneously Catalysed Synthesis of Ammonia 609
42.4 What else... 612
43 Recycling of Polymers: The Use of Waste 617
43.1 Thermal Cracking 618
43.2 Solvolysis 619
43.3 Hydrogenolyses 623
44 Homogeneous Catalysis with Renewables: Using Nature's Treasures 629
44.1 Catalytic Conversion of Oleochemicals 631
44.2 Catalytic Reactions of Terpenes 637
44.3 Catalytic Reactions of Carbohydrates 638
44.4 Catalytic Reactions of Lignin 640
45 Future Challenges of Homogeneous Catalysis: What the Crystal Ball Might Tell You 645
45.1 New Resources 645
45.2 New Reactions 655
45.3 New Smart Products 657
45.4 New Catalysts 658
45.5 New Methods 659
Epilogue 661
Answers to the Exercise Questions 663
Excursions Photo Credits 687
Index 691
Supplementary literature information can be found at www.wiley.com/go/behr/AHC 2
