Applied Homogeneous Catalysis

Applied Homogeneous Catalysis

By: Peter Neubert (author), Arno Behr (author), Axel Brehm (author)Paperback

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Description

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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About Author

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 Universitat 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.

Contents

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 C C 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

Product Details

  • publication date: 14/03/2012
  • ISBN13: 9783527326334
  • Format: Paperback
  • Number Of Pages: 716
  • ID: 9783527326334
  • weight: 1344
  • ISBN10: 3527326332

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