Applied Homogeneous Catalysis: A Tool for Sustainable Chemistry

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.

Table of 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 of CO 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

About the Author :
Arno Behr headed the Chair of Industrial Chemistry at TU Dortmund University, Germany, until his retirement in 2017. His research interests included homogeneous transition metal catalysis, conversion of petrochemicals and renewables, and catalyst recycling. Thomas Seidensticker leads a research group at TU Dortmund University, Germany. His research is dedicated to sustainable process design for homogeneous catalysts, including developing innovative recycling methods and converting renewable resources. Dieter Vogt is head of the Chair of Industrial Chemistry at TU Dortmund University, Germany, since 2017. His main research interests are homogeneous transition metal catalysis, ligand and catalyst design, and process development in continuously operated miniplants.