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Applied Homogeneous Catalysis

ISBN: 978-3-527-32641-9
716 pages
April 2012
Applied Homogeneous Catalysis (3527326413) cover image
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.
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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

Literature 25

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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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 Universität 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.
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“High recommended and excellent value in the paperback format.” (Organic Process Research and Development Journal, 2012)

 

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