- ISBN: 9783527326334 | 3527326332
- Cover: Paperback
- Copyright: 4/16/2012
Adopting a didactic approach at an advanced, masters level, this concise textbook provides an array of questions & answers and features numerous industrial case studies and examples, with references for further, more detailed reading and to the latest peer-reviewed articles at the end of each chapter. A significant feature is the book's treatment of more recently developed catalytic processes and their applications in the pharmaceutical and fine chemical industries, with an indication of their present and future commercial impact. Written by a dedicated lecturer with a wealth of experience in industry, this is an invaluable tool for practicing chemical engineers and chemists who need to advance their education in this vibrant and expanding field.
Arno Behr was born in 1952 in Aachen, Germany. He received his Diploma in chemistry from RWTH Aachen University and fi nished his PhD in 1979 under supervision of Prof. Willi Keim. After being employed at Henkel KGaA he is a full Professor of Technical Chemistry at Dortmund
University, Germany since 1996. Since 35 years his research interests cover homogeneous transition-metal catalysis, conversion of petrochemicals and renewables and catalyst recycling. During the last 30 years he became an experienced lecturer, held GDCh- and Dechema lectures and was involved in several advanced master and PhD courses.
Peter Neubert was born in 1981 in Castrop-Rauxel, Germany. He studied chemistry at Technische Universit?t Dortmund, Germany and Bergen University, Norway. He received his diploma in 2009 under the supervision of Professor Arno Behr. He is currently a doctoral candidate in the same group. His current research deals with the catalytic conversion of C5 materials and the development of recycling concepts in homogeneous catalysis.
University, Germany since 1996. Since 35 years his research interests cover homogeneous transition-metal catalysis, conversion of petrochemicals and renewables and catalyst recycling. During the last 30 years he became an experienced lecturer, held GDCh- and Dechema lectures and was involved in several advanced master and PhD courses.
Peter Neubert was born in 1981 in Castrop-Rauxel, Germany. He studied chemistry at Technische Universit?t Dortmund, Germany and Bergen University, Norway. He received his diploma in 2009 under the supervision of Professor Arno Behr. He is currently a doctoral candidate in the same group. His current research deals with the catalytic conversion of C5 materials and the development of recycling concepts in homogeneous catalysis.
Foreword V
Preface XIX
Abbreviations XXIII
Part I Chemical Basics 1
1 Definition, Options, and Examples: What Actually Is Catalysis? 3
1.1 Definition of Catalysis 3
1.2 The Different Varieties of Catalysis 5
1.3 The Directing Effect of the Catalyst 8
1.4 Catalysis as a Part of ‘‘Green Chemistry’’ 10
1.5 Sources of Information about Catalysis 10
Literature 14
2 A Brief History: Homogeneous Transition Metal Catalysis: A Young Science 17
2.1 A Brief History 17
3 Industrial Homogeneous Catalysis: What is the Economic Importance? 27
3.1 Application Areas of Catalysis 27
3.2 Important Homogeneous Catalyzed Processes 27
3.3 Synthesis of Fine Chemicals by Homogeneous Catalysis 28
Literature 32
4 Definitions of Important Terms: Selectivity, STY, TON, TOF, and More. . . 35
4.1 Conversion 35
4.2 Yield 36
4.3 Selectivity 37
4.4 Other Important Target Values 40
4.5 The Choice is Yours! 43
Literature 46
5 Bonds, Elemental Steps, and Catalyst Cycles: Basics of Organometallic Chemistry 47
5.1 Ligands 47
5.2 Change in Oxidation State 50
5.3 Changing of Coordination Number (CN) and Coordination Geometry 50
5.4 The Elementary Steps 51
5.5 Catalytic Cycles 57
Literature 60
6 Transition Metal Complexes: The ‘‘Captains’’ of Homogeneous Catalysis 63
6.1 Group IIIB Metals and Lanthanides 63
6.2 Metals of Group IVB 64
6.3 Metals of Groups VB to VIIB 64
6.4 The ‘‘Iron Metals’’ of Group VIII 65
6.5 The Noble Metals from Group VIII 65
6.6 Gold: A Noble Metal from Group IB 72
6.7 The Cost of Catalyst Metals 72
6.8 The Availability of Transition Metal Catalysts 74
6.9 A Typical Experiment: Synthesis of Pd(acac)2 75
Literature 76
7 The Complex Ligands: The ‘‘Mates’’ of Homogeneous Catalysis 79
7.1 Monodentate Ligand or Chelate? 79
7.2 Basicity of Ligands 82
7.3 Cone Angle (‘‘Tolman Cone Angle’’) 83
7.4 The Bite Angle 88
7.5 Costs and Accessibility of Ligands 91
7.6 A Typical Experiment: The Synthesis of Biphephos 93
7.7 Stability of Ligands 95
Literature 98
8 The Solvents: The Reaction Medium 101
8.1 Criteria for Choosing Solvents 102
8.2 Miscibility of Solvents 106
8.3 Solvents as Activators 107
8.4 Solvents as Deactivators 108
8.5 Availability and Purity of Solvents 109
8.6 Special Solvents 111
Literature 112
9 Asymmetric Catalysis: The ‘‘Special Case’’ 115
9.1 A Glossary of Asymmetric Catalysis 115
9.2 A Quick Look Back 119
9.3 Mechanistic Considerations 121
9.4 Chiral Ligands 125
9.5 Overview on Homogeneous Catalyzed Asymmetric Syntheses 127
9.6 Industrial Applications 127
Literature 131
10 Thermodynamics of Homogeneous Catalysis: When Does a Chemical Reaction Run? 133
10.1 Gibbs Energy and Energy Plot 133
10.2 Calculation or Assessment of the Free Reaction Enthalpy 135
10.3 Thermodynamic Analysis of Complex Reaction Systems 136
Literature 139
11 Kinetics of Homogeneous Catalysis: How Does the Reaction Proceed? 141
11.1 Frequently Occurring Kinetics 141
11.2 The Energy Diagram for Explaining Regioselectivity 145
11.3 The Energy Diagram for Explaining Enantioselectivity 146
11.4 Execution of Kinetic Measurements 146
11.5 A Concrete Example: The (Isomerizing) Hydroformylation of Octenes 147
11.6 Possible Failures in Kinetic Measurements 149
Literature 151
12 Overview on Spectroscopic Methods: Can We See into Homogeneous Catalysis? 153
12.1 UV/Visible Spectroscopy 153
12.2 IR Spectroscopy 155
12.3 NMR Spectroscopy 157
12.4 Mass Spectroscopy 162
12.5 Extended X-Ray Absorption Fine Structure Analysis 163
12.6 Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) 164
Literature 166
Part II Process Engineering Fundamentals 169
13 Reactor Types: Where Does Catalysis Occur? 171
13.1 Reactions in Homogeneous Liquid Phase 171
13.2 Fluid–Fluid Systems 174
13.3 The ‘‘Embarras de Richesses’’ 177
13.4 Pressure Reactors 180
13.5 New Trends 182
Literature 185
14 Overview on Catalyst Recycling Methods: Is My Catalyst Economical? 189
14.1 The Principles of Separation 189
14.2 Precipitation 193
14.3 Crystallization 196
14.4 Adsorption 196
Literature 199
15 Thermal Separation: The Simplest Removal of Volatile Products 203
15.1 The Basics 203
15.2 Example: Hydroformylation 204
15.3 Example: Oxidation of Ethene to Acetaldehyde 207
15.4 Example: Carbonylation of Methanol to Acetic Acid 209
Literature 212
16 Immobilization on Solid Supports: From Homogeneous to Heterogeneous 213
16.1 The Basic Principle 213
16.2 Organic Supports 214
16.3 Inorganic Supports 215
Literature 219
17 Liquid–Liquid Multiphase Systems: The Smart Approach to Catalyst Separation 223
17.1 Variants of Liquid–Liquid Biphasic (LLB) Systems 224
17.2 Reaction and Separation 225
17.3 Reactions with In-Situ Extraction 234
17.4 Reactions with Post Extraction 235
Literature 238
18 Thermomorphic Solvent Systems: Clever Enhancements 243
18.1 Thermoregulated Phase-Transfer Catalysis 243
18.2 Thermoregulated Microemulsions 245
18.3 Thermoregulated Fluorous Solvent Systems 246
18.4 Thermoregulated Polymer-Bound Catalysts 248
18.5 Thermomorphic Multicomponent Solvent Systems 251
18.6 A Retrospective Look at Catalyst Recycling Methods 253
Literature 256
Part III Homogeneous Catalyzed Reaction Types 259
19 An Overview of C–C-Bonding Reactions: A Guide Through the Jungle 263
Literature 270
20 Hydroformylations: The Industrial Route to Aldehydes and Alcohols 273
20.1 Substrates 274
20.2 Catalysts 275
20.3 Mechanisms 277
20.4 Industrial Processes 278
20.5 Asymmetric Hydroformylation 281
20.6 A Typical Experiment: Hydroformylation of 1-Octene 282
Literature 284
21 Carbonylations: The Versatile Insertions of Carbon Monoxide 291
21.1 Reactions between CO and Hydrogen 291
21.2 Reactions of CO with Alkenes and Vinyl Arenes 292
21.3 Reactions of CO with Dienes 293
21.4 Reactions of CO with Alkynes 295
21.5 Reactions of CO with Alcohols 296
21.6 A Typical Experiment 298
Literature 300
22 Oligomerization and Cyclooligomerization: The Conversion of Unsaturated Aliphatics into Short Chains or Medium-Sized Rings 303
22.1 Oligomerization of Alkenes 303
22.2 Dienes 311
22.3 Alkynes 313
22.4 Cooligomerizations 314
22.5 A Typical Experiment 316
Literature 318
23 Metathesis: A ‘‘Change-Your-Partners’’ Dance 323
23.1 Mechanism and Catalysts 325
23.2 Industrial Applications 330
23.3 A Typical Experiment: Self Metathesis of 1-Octene 332
Literature 334
24 Polymerizations: The Purposeful Assembly of Macromolecules 337
24.1 Polyethylene and Ziegler Catalysts 337
24.2 Polypropylene and Metallocene Catalysis 341
24.3 Further Polyolefins 346
24.4 Polydienes 347
24.5 Polyketones 348
24.6 Polyalkynes 349
24.7 Post-Metallocenes 350
24.8 Current Topics in Polymer Research 351
24.9 A Typical Experiment 352
Literature 354
25 Telomerizations: The Construction of C8 and C10 Chains 359
25.1 Reactions, Mechanisms, and Catalysts 359
25.2 Butadiene Telomerizations 362
25.3 Telomerizations with Isoprene 371
25.4 Telomerizations in Liquid–Liquid Biphasic Systems 372
25.5 A Typical Experiment 374
Literature 376
26 Reactions with Carbon Dioxide: The Activation of an ‘‘Inactive’’ Molecule 381
26.1 Carbon Dioxide and Alkanes 382
26.2 Carbon Dioxide and Alkenes 383
26.3 Carbon Dioxide and Dienes 384
26.4 Carbon Dioxide and Alkynes 387
26.5 Carbon Dioxide and Aromatics 388
26.6 Carbon Dioxide and Hydrogen 388
26.7 Carbon Dioxide and Epoxides 392
26.8 Carbon Dioxide and Amines 393
26.9 Carbon Dioxide-Containing Polymers 394
26.10 A Typical Experiment 396
Literature 398
27 Carbon–Carbon Coupling with Aromatics: New Name Reactions 403
27.1 Mizoroki–Heck Reactions 404
27.2 Sonogashira–Hagihara Reactions 406
27.3 Suzuki–Miyaura Reaction 407
27.4 Cross-Couplings with Metal Organyles 409
27.5 A Typical Experiment 411
Literature 413
28 Hydrogenations: C–H Bond Formation 419
28.1 Catalysts and Mechanisms 419
28.2 Asymmetric Hydrogenation 420
28.3 Hydrogenation of Various Functional Groups 422
28.4 Technical Applications 426
28.5 A Typical Experiment 431
Literature 432
29 Oxidations: Formation of C–O Bonds 437
29.1 Wacker Oxidations 437
29.2 Epoxidations 440
29.3 Asymmetric Dihydroxylations 444
29.4 Oxidative Cleavage of C¼C Double Bonds 444
29.5 Oxidations of Alkyl Aromatics 446
29.6 A Typical Experiment 448
Literature 449
30 Aminations: Formation of C–N Bonds 455
30.1 Amination of Aryl Halides 455
30.2 Hydroamination of Alkenes 458
30.3 Hydroaminations of Dienes 461
30.4 Hydroamination of Alkynes 462
30.5 Amination of Functional Groups 462
30.6 . . .Some More Aminations 463
30.7 A Typical Experiment 464
Literature 466
31 Isomerizations: Migration of Double Bonds and Rearrangement of the Carbon Backbone 473
31.1 Isomerization of Alkenes 473
31.2 Isomerization of Substituted Alkenes 475
31.3 Rearrangement of the Backbone 478
31.4 A Typical Experiment 479
Literature 480
Part IV New Trends 485
32 Tandem Reactions: Multiple Synthesis Steps in One Pot 487
32.1 Multicomponent Reactions 488
32.2 Multifunctional Catalysis 489
32.3 Tandem and Related Reactions 491
32.4 A Typical Experiment 497
Literature 500
33 Combinatorial Chemistry and High-Throughput Catalyst Screening: The Fast Way to Optimum Results 507
33.1 Basics and Definitions 507
33.2 Parallel Reactor Systems 509
33.3 Sequential Reactor Systems 514
Literature 517
34 Green Solvents: Working with Eco-Friendly Solvents 521
34.1 Ionic Liquids 521
34.2 Supercritical Fluids 526
34.3 Fluorous Solvents 529
34.4 Polyethers 530
34.5 Conclusions 531
Literature 533
35 Alkane Activations: Acquisitions of New Feedstocks 541
35.1 Mechanistic Considerations 542
35.2 Alkane Oxidations 543
35.3 Alkane Carbonylations 545
35.4 Alkane Metathesis 545
35.5 Alkane Hydrogenolysis 546
35.6 Alkane Borylation 546
35.7 Alkane Sulfonation 547
35.8 A Look Back 547
Literature 548
36 More Efficient Ligands: The Best is the Enemy of the Good 553
36.1 Nitrogen-Containing Ligands 554
36.2 Unusual Phosphorus Ligands 556
36.3 Ligands Containing Elements from Group VIA 557
36.4 Ligands Containing Elements from Group IVA 559
Literature 562
37 Nanocatalysis: Between Homogeneous and Heterogeneous Catalysis 569
37.1 Synthesis and Properties of Nanocatalysts 569
37.2 Stabilization of Nanoparticles 571
37.3 Heterogenization of Nanoparticles on Solid Supports 574
37.4 Catalysis Involving Metal Nanoparticles 574
Literature 576
38 Homogeneous Catalysis with Renewables: Using Nature.s Treasures 583
38.1 Catalytic Conversion of Fatty Compounds 585
38.2 Catalytic Reactions of Carbohydrates 593
38.3 Catalytic Reactions of Terpenes 594
Literature 597
39 Electrocatalysis/Sonocatalysis/Photocatalysis/Microwave/Extreme Pressure: Alternative Methods of Activation 603
39.1 Electrocatalysis 603
39.2 Photocatalysis 605
39.3 Sonocatalysis 606
39.4 Microwave Catalysis 608
39.5 Extreme High-Pressure Catalysis 611
Literature 613
40 Process Development in Miniplants: From Laboratory to Production 621
40.1 Miniplant with Continuously Stirred-Tank Reactor (Miniplant I) 622
40.2 Miniplant with Loop Reactor and Phase Separator (Miniplant II) 623
40.3 Miniplant with Jetloop Reactor and Phase Separator (Miniplant III) 626
40.4 Miniplant with a Mixer–Settler Battery (Miniplant IV) 628
Literature 631
41 The Future of Homogeneous Catalysis: A Look Ahead 633
41.1 New Resources 633
41.2 New Reactions 638
41.3 New Catalysts 641
41.4 New Methods 643
Literature 644
Answers to the Quickies 645
Index 669
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