Catalysis Books

Book SynopsisThere are many mononuclear iron containing enzymes in nature that utilize molecular oxygen and transfer one or both oxygen atoms of O2 to substrates. These enzymes catalyze many processes including the biosynthesis of hormones, the metabolism of drugs, DNA and RNA base repair and, the biosynthesis of antibiotics. Therefore, mononuclear iron containing enzymes are important intermediates in bioprocesses and have great potential in the commercial biosynthesis of specific products since they often catalyze reactions regioselectively or stereospecifically. Understanding their mechanism and function is important and will assist in searches for commercial exploitation. In recent years, advances in experimental as well as theoretical methodologies have made it possible to study the mechanism and function of these enzymes and much information on their properties has been gained. This book highlighting recent developments in the field is, therefore, a timely addition to the literature and will interest a broad readership in the fields of biochemistry, inorganic chemistry and computational chemistry. The Editors, leaders in the field of nonheme and heme iron containing monoxygenases, have filled the book with topical review chapters by leaders in the various sub-disciplines.Table of ContentsNonheme iron(IV)-oxo oxidants in enzymes: Spectroscopic properties and reactivity patterns; Heme iron(IV)-oxo oxidants in enzymes: Spectroscopic properties and reactivity patterns; Mechanism and function of taurine/ -ketoglutarate dioxygenase enzymes, an update; Mechanism and function of cysteine dioxygenase enzymes; Mechanism and function of heme peroxidase enzymes; Mechanism and function of cytochrome P450 enzymes Biomimetic studies of mononuclear nonheme iron containing oxidants; Biomimetic studies of mononuclear porphyrin containing oxidants; Density functional calibration studies on iron-containing systems; Density functional theory studies on isomerisation reactions catalyzed by cytochrome P450 enzymes Quantum mechanics/molecular mechanics studies of peroxidase enzymes; Theoretical modelling of nonheme iron containing oxidants

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Book SynopsisNow in it's 3rd Edition, Industrial Catalysis offers all relevant information on catalytic processes in industry, including many recent examples. Perfectly suited for self-study, it is the ideal companion for scientists who want to get into the field or refresh existing knowledge.The updated edition covers the full range of industrial aspects, from catalyst development and testing to process examples and catalyst recycling. The book is characterized by its practical relevance, expressed by a selection of over 40 examples of catalytic processes in industry. In addition, new chapters on catalytic processes with renewable materials and polymerization catalysis have been included. Existing chapters have been carefully revised and supported by new subchapters, for example, on metathesis reactions, refinery processes, petrochemistry and new reactor concepts. "I found the book accesible, readable and interesting - both as a refresher and as an introduction to new topics - and a convenient first reference on current industrial catalytic practise and processes." Excerpt from a book review for the second edition by P. C. H. Mitchell, Applied Organometallic Chemistry (2007)Trade Review"This is the third addition of Jens Hagen�s overview of the industrial application of catalytic science and engineering. As with previous editions this work covers a wide range of catalytic processes spanning heterogeneous and homogeneous catalysis, including chapters on biocatalysis and electrocatalysis. This edition has been extensively revised and includes additions not present in earlier versions. A key feature of the text is inclusion of exercises in each chapter, with solutions provided...[This book] would...be a useful reference for an introductory undergraduate course on catalysis, for whom the exercises would be particularly valuable, or to a researcher starting out in area unfamiliar to them... ...an excellent overview of catalysis and its applications more broadly..."(AOC review March 2017)Table of ContentsPreface to the Third Edition XV Abbreviations XVII 1 Introduction 1 1.1 The Phenomenon Catalysis 1 1.2 Mode of Action of Catalysts 2 1.2.1 Activity 4 1.2.1.1 Turnover Frequency TOF 6 1.2.1.2 Turnover Number TON 7 1.2.2 Selectivity 7 1.2.3 Stability 8 1.2.4 Mole Balance and Conversion 8 1.3 Classification of Catalysts 10 1.4 Comparison of Homogeneous and Heterogeneous Catalysis 11 Exercises 14 References 15 2 Homogeneous Catalysis with Transition Metal Catalysts 17 2.1 Key Reactions in Homogeneous Catalysis 18 2.1.1 Coordination and Exchange of Ligands 18 2.1.2 Complex Formation 20 2.1.3 Acid–Base Reactions 22 2.1.4 Redox Reactions: Oxidative Addition and Reductive Elimination 23 2.1.4.1 Oxidative Coupling and Reductive Cleavage 27 2.1.5 Insertion and Elimination Reactions 28 2.1.5.1 β-Elimination 30 2.1.5.2 α-Elimination 30 2.1.6 Reactions at Coordinated Ligands 31 2.2 Catalyst Concepts in Homogeneous Catalysis 32 2.2.1 The 16/18-Electron Rule 32 2.2.2 Catalytic Cycles 34 2.3 Characterization of Homogeneous Catalysts 35 2.3.1 Infrared Spectroscopy 38 2.3.2 NMR Spectroscopy 40 Exercises 42 References 45 3 Homogeneously Catalyzed Industrial Processes 47 3.1 Overview 47 3.2 Examples of Industrial Processes 48 3.2.1 Oxo Synthesis 50 3.2.2 Production of Acetic Acid by Carbonylation of Methanol 52 3.2.3 Selective Ethylene Oxidation by theWacker Process 55 3.2.4 Oxidation of Cyclohexane 57 3.2.5 Suzuki Coupling 58 3.2.6 Oligomerization of Ethylene (SHOP Process) 59 3.2.7 Telomerization of Butadiene 61 3.2.8 Adipodinitrile 63 3.3 Asymmetric Catalysis 63 3.3.1 Introduction 63 3.3.2 Catalysts 64 3.3.3 Commercial Applications 65 3.3.3.1 Asymmetric Hydrogenation 65 3.3.3.2 Enantioselective Isomerization: L-Menthol 67 3.3.3.3 Asymmetric Epoxidation 68 3.4 Alkene Metathesis 69 3.4.1 Examples of Heterogeneous Catalysis 72 3.5 Recycling of Homogeneous Catalysts 73 3.5.1 Overview 73 3.5.1.1 Precipitation of the Catalyst or of the Product(s) 73 3.5.1.2 Thermal Separation 73 3.5.1.3 Membrane Separation 73 3.5.1.4 Adsorption 74 3.5.1.5 Phase Separation/Extraction 74 3.5.2 Reactions in Two-Phase Liquid–Liquid Systems 74 Exercises 76 References 78 4 Biocatalysis 81 4.1 Introduction 81 4.1.1 Active Sites 83 4.1.2 Coenzymes 84 4.2 Kinetics of Enzyme-Catalyzed Reactions 84 4.3 Industrial Processes with Biocatalysts 90 4.3.1 Acrylamide from Acrylonitrile 90 4.3.2 Aspartame Through Enzymatic Peptide Synthesis 91 4.3.3 L-Amino Acids by Aminoacylase Process 92 4.3.4 Pharmaceuticals 93 4.3.5 Herbicides 95 4.3.5.1 4-Hydroxyphenoxypropionic Acid as Herbicide Intermediate 96 Exercises 97 References 97 5 Heterogeneous Catalysis: Fundamentals 99 5.1 Individual Steps in Heterogeneous Catalysis 99 5.2 Kinetics and Mechanisms of Heterogeneously Catalyzed Reactions 101 5.2.1 The Importance of Adsorption in Heterogeneous Catalysis 102 5.2.2 Kinetic Treatment 106 5.2.3 Mechanisms of Heterogeneously Catalyzed Gas-Phase Reactions 108 5.2.3.1 Langmuir–Hinshelwood Mechanism (1921) 109 5.2.3.2 Eley–Rideal Mechanism (1943) 111 5.3 Catalyst Concepts in Heterogeneous Catalysis 113 5.3.1 Energetic Aspects of Catalytic Activity 113 5.3.2 Steric Effects 124 5.3.3 Electronic Factors 134 5.3.3.1 Redox Catalysts 134 5.3.3.2 Acid/Base Catalysts (Ionic Catalysts) 135 5.3.3.3 Metals 136 5.3.3.4 Bimetallic Catalysts 140 5.3.3.5 Semiconductors 144 5.3.3.6 Insulators: Acidic and Basic Catalysts 157 5.4 Catalyst Performance 164 5.4.1 FactorsWhich Affect the Catalyst Performance 164 5.4.2 Supported Catalysts 166 5.4.3 Promoters 172 5.4.4 Inhibitors 176 5.5 Catalyst Deactivation 177 5.5.1 Catalyst Poisoning 179 5.5.2 Poisoning of Metals 179 5.5.3 Poisoning of Semiconductor Oxides 182 5.5.4 Poisoning of Solid Acids 182 5.5.5 Deposits on the Catalyst Surface 183 5.5.6 Thermal Processes and Sintering 185 5.5.7 Catalyst Losses via the Gas Phase 186 5.6 Regeneration and Recycling of Heterogeneous Catalysts 186 5.7 Characterization of Heterogeneous Catalysts 189 5.7.1 Physical Characterization 190 5.7.1.1 Temperature-Programmed Desorption 195 5.7.2 Chemical Characterization and Surface Analysis 195 5.7.2.1 Temperature-Programmed Reaction Methods 196 5.7.2.2 Transmission Electron Microscopy 197 5.7.2.3 Low-Energy Electron Diffraction (LEED) 198 5.7.2.4 IR Spectroscopy 199 5.7.2.5 Electron Spectroscopy for Chemical Analysis (ESCA) 199 5.7.2.6 Auger Electron Spectroscopy (AES) 201 5.7.2.7 Ion Scattering Spectroscopy (ISS) 201 5.7.2.8 Secondary Ion Mass Spectrometry (SIMS) 202 Exercises 203 References 209 6 Catalyst Shapes and Production of Heterogeneous Catalysts 211 6.1 Introduction 211 6.2 Bulk Catalysts 212 6.2.1 Precipitation 212 6.2.2 Fusion and Alloy Leaching 214 6.2.3 Sol–Gel Synthesis 215 6.2.4 Flame Hydrolysis 217 6.2.5 Hydrothermal Synthesis 217 6.2.6 Heteropolyacids 219 6.3 Supported Catalysts 219 6.3.1 Impregnation 220 6.3.2 Coprecipitation 225 6.3.3 Adsorption/Ion-Exchange 226 6.3.3.1 Ion-Exchange Resins 227 6.3.4 Anchoring/Grafting 228 6.3.5 Monolithic Catalysts 229 6.4 Shaping of Catalysts and Catalyst Supports 230 6.5 Immobilization of Homogeneous Catalysts 232 6.5.1 Supported Solid-Phase Catalysts (SSPC) 234 6.5.2 Supported Liquid-Phase Catalysts (SLPC) 236 6.5.3 Encapsulation 236 Exercises 237 References 238 7 Shape-Selective Catalysis: Zeolites 239 7.1 Composition and Structure of Zeolites 239 7.2 Catalytic Properties of the Zeolites 242 7.2.1 Shape Selectivity 243 7.2.1.1 Reactant Selectivity 243 7.2.1.2 Product Selectivity 246 7.2.1.3 Restricted Transition State Selectivity 246 7.2.2 Acidity of Zeolites 247 7.3 Isomorphic Substitution of Zeolites 251 7.4 Metal-Doped Zeolites 252 7.5 Applications of Zeolites 255 Exercises 258 References 259 8 Heterogeneously Catalyzed Processes in Industry 261 8.1 Overview 261 8.1.1 Production of Inorganic Chemicals 261 8.1.2 Production of Organic Chemicals 261 8.1.3 Refinery Processes 262 8.1.4 Catalysts in Environmental Protection 264 8.2 Examples of Industrial Processes – Bulk Chemicals 266 8.2.1 Ammonia Synthesis 266 8.2.2 Hydrogenation 268 8.2.3 Methanol Synthesis 270 8.2.4 Selective Oxidation of Propene 272 8.2.4.1 Oxidation of Propene with H2O2 to Propylene Oxide 277 8.2.5 Selective Oxidation of Hydrocarbons 277 8.2.5.1 n-Butane to Maleic Anhydride 278 8.2.5.2 o-Xylene to Phthalic Anhydride 280 8.3 Fine Chemicals Manufacture 281 8.3.1 Fine Chemicals andTheir Synthesis 281 8.3.2 Selected Examples of Industrial Processes 285 8.3.2.1 Hydrogenation 286 8.3.2.2 Oxidation 288 8.3.2.3 Catalytic C–C Linkage 290 8.3.2.4 Acid/Base Catalysis 292 Exercises 294 References 297 9 Refinery Processes and Petrochemistry 299 9.1 Hydrotreating 300 9.2 Catalytic Cracking 302 9.3 Hydrocracking 304 9.4 Catalytic Reforming 306 9.5 Alkylation 307 9.6 Hydroisomerization 308 9.7 Synthesis Gas and Hydrogen by Steam Reforming 310 9.8 Natural Gas Conversion to Fuels and Chemicals 312 9.9 Fischer–Tropsch Synthesis 313 9.10 Etherification Reactions 315 Exercises 316 References 317 10 Electrocatalytic Processes 319 10.1 Comparison Between Electrocatalysis and Heterogeneous Catalysis 319 10.2 Electroorganic Syntheses 319 10.2.1 Electrocatalytic Hydrogenation 320 10.2.2 Electrocatalytic Oxidation 322 10.2.3 Electrochemical Addition 323 10.3 Electrocatalysis in Fuel Cells 324 10.3.1 Basic Principles 324 10.3.2 Types of Fuel Cell and Catalyst 325 10.3.3 Important Reactions in Fuel Cell Technology 328 10.3.3.1 The Anodic Reaction 328 10.3.3.2 The Cathodic Reaction 329 10.3.3.3 Methanol Oxidation 331 Exercises 332 References 333 11 Environmental Catalysis and Green Chemistry 335 11.1 Automotive Exhaust Catalysis 335 11.2 NOx Removal Systems 338 11.2.1 Selective Catalytic Reduction of Nitrogen Oxides 338 11.2.2 NOx Storage-Reduction Catalyst for Lean-Burning Engines 340 11.3 Catalytic Afterburning 341 11.4 Green Chemistry and Catalysis 344 11.4.1 Examples of Catalytical Processes 345 11.4.1.1 Aldol Condensation 345 11.4.1.2 Diels–Alder Reaction 346 11.4.1.3 Hydrogenation 347 11.4.1.4 Cyclization inWater 347 11.4.1.5 Use of Ionic Liquids 347 11.4.1.6 Green Solvents 349 Exercises 350 References 351 12 Phase-Transfer Catalysis 353 12.1 Definition 353 12.2 Catalysts for PTC 353 12.3 Mechanism and Benefits of PTC 354 12.4 PTC Reactions 355 12.5 Selected Industrial Processes with PTC 356 12.5.1 Continuous Dehydrohalogenation to Produce the Large-Scale Monomer Chloroprene 356 12.5.2 Polycarbonate Manufacture with Phosgene 356 12.5.3 Etherification (O-Alkylation) 357 12.5.4 Aldehydes by Oxidation of Alcohols with Hypochlorite 357 12.5.5 Carbonylation 357 12.5.6 2-Phenylbutyronitrile by Alkylation 358 Exercises 359 References 359 13 Catalytic Processes with Renewable Materials 361 13.1 Biofuels 361 13.2 Biorefinery 366 13.2.1 Lignocellulose Feedstock Biorefinery 368 13.3 Chemicals from Biomass 369 13.3.1 Chemicals from Biomass via Platform Molecules 369 13.3.1.1 Carbohydrates 369 13.3.1.2 Fats and Oils 373 13.3.1.3 Terpenes 375 13.3.2 Direct Biomass Conversion to End-Products 376 Exercises 378 References 378 14 Polymerization Catalysis 381 14.1 Introduction 381 14.2 Fundamentals of Catalytical Polymerization Processes 381 14.3 Coordination Polymerization 383 14.3.1 Ziegler–Natta Catalysts 383 14.3.1.1 Heterogeneous Ziegler–Natta Catalysts 384 14.3.1.2 Homogeneous Ziegler–Natta Catalysts 386 14.3.1.3 Metallocenes 386 14.3.1.4 Ring-OpeningMetathetic Polymerization 388 14.4 Examples of Catalytical Polymerization Processes 389 14.4.1 Polyethylene Production 389 14.4.2 Polypropylene Production 391 Exercises 392 References 393 15 Planning, Development, and Testing of Catalysts 395 15.1 Stages of Catalyst Development 395 15.2 Development of a Catalytical Process: Hydrogenation of Benzene to Cyclohexane 398 15.3 Selection and Testing of Catalysts in Practice 401 15.3.1 Catalyst Screening 401 15.3.2 Catalyst Test Reactors and Kinetic Modeling 405 15.3.2.1 Differential Reactor 405 15.3.2.2 Differential Circulating Reactor 407 15.3.2.3 Integral reactor 411 15.3.3 Kinetic Modeling and Simulation 416 15.3.3.1 Hydrogenation of Benzaldehyde 416 15.3.3.2 Modeling of a Trickle Bed Reactor 420 15.3.4 Catalyst Discovery via High-Throughput Experimentation 427 Exercises 430 References 430 16 Catalysis Reactors 433 16.1 Plug Flow Reactor (PFR) 433 16.2 Continuous Stirred-Tank Reactor (CSTR) 435 16.3 Reactor Calculations 436 16.4 Two-Phase Reactors 440 16.4.1 Single-Bed Reactor 441 16.4.2 Multibed Reactor 441 16.4.3 Multitubular Reactors 442 16.4.4 Shallow-Bed Reactors 442 16.4.5 Fluidized-Bed Reactors 443 16.5 Three-Phase Reactors 443 16.5.1 Fixed-Bed Reactors 445 16.5.2 Suspension Reactors 447 16.6 Reactors for Homogeneously Catalyzed Reactions 451 16.7 New Reactor Concepts 452 16.7.1 Membrane Reactors 452 16.7.2 Catalytic Reactive Distillation 453 16.7.3 Catalytic Microreactors 454 Exercises 455 References 457 17 Economic Importance of Catalysts 459 References 462 18 Future Development of Catalysis 463 18.1 Homogeneous Catalysis 463 18.2 Heterogeneous Catalysis 465 18.2.1 Use of Other Cheaper Raw Materials 467 18.2.2 Catalysts for Energy Generation 468 18.2.3 Better Strategies for Catalyst Development 469 References 472 Solutions to the Exercises 473 Index 513

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Book SynopsisIn chemistry, photocatalysis refers to the acceleration of a photoreaction in the presence of a catalyst. Various aspects and applications of this process are described in the six chapters of this book. Chapter One addresses the reduction and oxidation of heavy metals by the photocatalytic process to produce less toxic forms, thus reducing pollution. Chapter Two reviews some issues of photocatalytic reactions which may have been overlooked in other reports. Chapter Three deals with the utilisation of ZnO-CdO nanoblocks as adsorbent and efficient solar photocatalysts towards brilliant cresol blue degradation. Chapter Four explains heterogeneous photocatalysis through the use of titanium and tungsten oxide nanostructures. Chapter Five reports the fabrication and evaluation of TiO2 nanowires supported on graphene and sensitised with Ag in a unique hierarchical three-dimensional sandwich structure. Lastly, Chapter Six provides an overview of recent achievements in C-N bond formation reactions triggered by visible light-induced DDQ-photoredox catalysis.Table of ContentsPreface; Oxidation and Reduction of Heavy Metals by Photocatalytic Processes; Peculiarities of the Reactions on Particulate Photocatalysts; ZnO-CdO Nanoblocks: Utilization as Adsorbent and Efficient Solar Photo-Catalyst towards Brilliant Cresol Blue Degradation; Heterogeneous Photocatalysis Explained through the Use of Titanium and Tungsten Oxide Nanostructures; Designing an Enhanced Visible-Light Activated Hierarchical Three-Dimensional Ag/TIO2 Nanowires/Graphene Sandwich Photocatalyst; Visible Light-Mediated DDQ Photoredox-Catalyzed C-N Bond Formation Reactions: A Review; Index.

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Book SynopsisCatalysis is a multidisciplinary subject. This book introduces the chemical, materials, and engineering principles of catalysis so that both MSc and PhD students with a basic but not extensive knowledge of chemistry and physics and those with a basic understanding of chemical engineering can learn more about catalysis. Examples are taken from catalytic reactions and catalysts used in the energy, petroleum, and base-chemicals industry.The second edition differs from the first edition in the way basic topics are integrated with catalytic applications. The authors introduce two new chapters: 'Cleaning of Fuels by Hydrotreating' and 'Electrocatalysis'. Hydrotreating is a very important industrial process and offers the opportunity to discuss metal sulfide catalysts. Electrocatalysis gains more and more attention because it can be used to minimize the anthropogenic CO₂ emissions. Solar, wind, and hydroelectricity can drive water electrolysis and CO₂ electroreduction and, therefore, excess renewable electricity can be stored in chemicals.Introduction to Heterogeneous Catalysis (Second Edition) is intended for a one-semester course for master and PhD students who want to learn more about the principles of catalysis. This must-read textbook will enable students to read catalysis literature without much difficulty and presents not only the basic concepts of catalysis but integrates the chemical, materials, and engineering aspects of catalysis with industry examples.

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Book SynopsisCatalysis is a multidisciplinary subject. This book introduces the chemical, materials, and engineering principles of catalysis so that both MSc and PhD students with a basic but not extensive knowledge of chemistry and physics and those with a basic understanding of chemical engineering can learn more about catalysis. Examples are taken from catalytic reactions and catalysts used in the energy, petroleum, and base-chemicals industry.The second edition differs from the first edition in the way basic topics are integrated with catalytic applications. The authors introduce two new chapters: 'Cleaning of Fuels by Hydrotreating' and 'Electrocatalysis'. Hydrotreating is a very important industrial process and offers the opportunity to discuss metal sulfide catalysts. Electrocatalysis gains more and more attention because it can be used to minimize the anthropogenic CO₂ emissions. Solar, wind, and hydroelectricity can drive water electrolysis and CO₂ electroreduction and, therefore, excess renewable electricity can be stored in chemicals.Introduction to Heterogeneous Catalysis (Second Edition) is intended for a one-semester course for master and PhD students who want to learn more about the principles of catalysis. This must-read textbook will enable students to read catalysis literature without much difficulty and presents not only the basic concepts of catalysis but integrates the chemical, materials, and engineering aspects of catalysis with industry examples.

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Book SynopsisThe field of computational catalysis has existed in one form or another for at least 30 years. Its ultimate goal - the design of a novel catalyst entirely from the computer. While this goal has not been reached yet, the 21st Century has already seen key advances in capturing the myriad complex phenomena that are critical to catalyst behaviour under reaction conditions. This book presents a comprehensive review of the methods and approaches being adopted to push forward the boundaries of computational catalysis. Each method is supported with applied examples selected by the author, proving to be a more substantial resource than the existing literature. Both existing a possible future high-impact techniques are presented. An essential reference to anyone working in the field, the book's editors share more than two decade's of experience in computational catalysis and have brought together an impressive array of contributors. The book is written to ensure postgraduates and professionals will benefit from this one-stop resource on the cutting-edge of the field.Table of ContentsCharge transfer or reactive potentials; Ab initio thermodynamics; First-principles based microkinetic modelling; Adaptive kinetic Monte Carlo; Computational catalyst screening; Enantioselective catalysis; Dynamics of Surface Reactions; Advances in DFT functionals for catalysis; Modelling highly correlated systems in heterogeneous catalysis

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Book SynopsisThis book aims to introduce the basic concepts involved in industrial catalytic processes. It is profusely illustrated with experimental results with the main objective of guiding how to select a suitable catalyst for specific processes. The book is divided in two parts. In the first part the basic concepts are addressed, regarding the existing theories, activity patterns and adsorption-desorption phenomena. In the second part the key experimental methods for the physicochemical characterization of catalysts are presented, as well as the currently used catalyst pre and post treatments. The last chapter describes some important in situ characterization techniques (e.g. XPS and TEM) and surface model patterns related to surface modifications occurring during the reaction. Thoroughly illustrated with microscopy images, spectroscopy data and schematics of reaction mechanisms, the book provides a powerful learning tool for students in undergraduate and graduate level courses on the field of catalysis. Exercises and resolved problems are provided, as well as experimental procedures to support laboratory classes. Furthermore, the content is presented in a carefully chosen sequence, reflecting the 30 year teaching experience of the author. The author, Professor Martin Schmal, sees the present book as a way of conveying basic knowledge needed for the development of more efficient catalysts (i.e. nanostructured materials) and novel industrial chemical processes in the fields of environmental chemistry, fine chemistry, hydrotreating of heavy oils, hydrogen production and biomass processing.Table of ContentsIntroduction on Heterogeneous Catalysis.- Model a catalyst.- Activity Patterns.- Adsorption-desorption.- Basic concepts.- Surface area and volume.- Catalysts preparation.- Variables influencing the final properties of the catalyst.- Structural analyses – x- ray diffraction.- Spectroscopy in the Infrared Region.- X-ray photoelectron spectroscopy (ESCA – XPS/ISS).- Electronic Microscopy: General and Specific Notions.- Nanostructured catalysts.- Kinetics and mechanisms.- Evaluation of Industrial Catalysts.

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Book SynopsisIn the past 12 years since its publication, Concepts of Modern Catalysis and Kinetics has become a standard textbook for graduate students at universities worldwide. Emphasizing fundamentals from thermodynamics, physical chemistry, spectroscopy, solid state chemistry and quantum chemistry, it introduces catalysis from a molecular perspective, and stresses how it is interwoven with the field of reaction kinetics. The authors go on to explain how the world of reacting molecules is connected to the real world of industry, by discussing the various scales (nano - micro - macro) that play a role in catalysis. Reflecting the modern-day focus on energy supplies, this third edition devotes attention to such processes as gas-to-liquids, coal-to-liquids, biomass conversion and hydrogen production. From reviews of the prior editions: 'Overall, this is a valuable book that I will use in teaching undergraduates and postgraduates.' (Angewandte Chemie - I. E.) '...this excellent book is highly recommended to students at technical universities, but also entrants in chemical industry. Furthermore, this informative handbook is also a must for all professionals in the community.' (AFS) 'I am impressed by the coverage of the book and it is a valuable addition to the catalysis literature and I highly recommend purchase' (Energy Sources) Trade ReviewFrom Reviews of former editions: '... such an enterprise will be of great value to the community, to professionals as well as graduate and undergraduate students attempting to move into the field of modern catalysis and kinetics. I strongly recommend you publish this book based on the proposal.' - Prof. Dr. G. A. Samorjai, University of California 'Both authors are well respected specialists, with a very long record of original top-quality work and an international reputation. A book from these authors will be considered an authoritative piece of work, I definitely support this project and I am looking forward to use the book when published.' - Prof. Dr. D. E. Resasco, University of Oklahoma 'I wholly support the proposed project. The authors are very competent young colleagues and there is a real need for such a textbook' - Prof. Dr. G. Ertl, Fritz-Haber-Institut, Max-Planck-Gesellschaft, Berlin "I am impressed by the coverage of the book and it is a valuable addition to the catalysis literature and I highly recommend purchase" Energy Sources "The book's structure is based on academic courses taught over the years by the two authors. Questions and exercises are offered at the end of the book. Highly recommended." Choice "...this excellent book is highly recommended to students at technical universities, but also entrants in chemical industry. Furthermore, this informative handbook is also a must for all professionals in the community." AFS "The text is well written and easy to follow, with references provided for the reader who wants to know more. The text is enlivened by snippets of information and comment... If you are looking for a good textbook on heterogeneous catalysis, "Concepts of Modern Catalysis and Kinetics" is well worth considering. It is certainly a book I would have liked to have read when I started in catalysis research." Platinum Metals Review "The authors are experienced experts, who have a fundamental understanding of catalysis - from its theoretical-chemical and physical-chemical basics right up to applications in process technology. I wholeheartedly recommend this book to anyone seeking a solid basis in the field of catalysis." Chemie Ingenieur Technik "In summary "Concepts of Modern Catalysis and Kinetics" is a valuable guide to enter and travel the sometimes rather labyrinthine trails in heterogeneous catalysis. " ChemPhysChem "The book is well written and richly illustrated with instructive black and white diagrams. Students, especially those at Eindhoven and Lyngby, will have to read it from cover to cover. More mature readers, such as myself, have the privilege to skip the dry bits on kinetics and focus on the catalysis parts for the sheer excitement of the facts... The book does catalysis justice as a central concept of chemistry." Chemistry & Industry "This book is a thorough and comprehensive introduction to the science and application of heterogeneous catalysis." Applied Organometallic Chemistry "This book will be a valuable addition to many chemistry libraries... For the specialist in heterogeneous catalysis, the book provides a wealth of information regarding both fundamentals and applications." Synthesis"... von Herrn Niemantsverdriet habe ich bereits mehrere Bücher rezensiert und natürlich auch gelesen. Er schreibt interessant und versteht es, aktuelle Entwicklungen mit dem klassischen Wissen zu verbinden. ..." Dr. habil. J. Caro, Institut für Angewandte Chemie, Berlin "... das vorgeschlagene Buchprojekt wird von mir nachdrücklich unterstützt. Die beiden Autoren sind kompetente Kollegen und für ein derartiges Lehrbuch besteht ein echter Bedarf." Prof. Dr. G. Ertl, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin "Die Autoren dieses Werkes haben einen hervorragenden Ausweg gefunden, auf den bereits der Titel hinweist: Anstatt zu versuchen, einen vollständigen Überblick zu liefern - was ohnehin zum Scheitern verurteilt wäre - erläutern sie die Konzepte, die den gegenwärtigen Stand der Katalyseforschung widerspiegeln. Das Ergebnis ist eine hervorragende Einführung in die heterogene Katalyse, die für den fortgeschrittenen Studenten und den erfahrenen Fachwissenschaftler gleichermaßen wertvoll ist... Man kann dieses Buch ohne Einschränkung empfehlen. Die Katalyseforschung ist kein reifes Gebiet in dem Sinne, dass eine nahezu geschlossene Theorie aller wichtigen Phänomene besteht. Sie ist im Gegenteil mitten in der Entwicklung begriffen, und dieser Aspekt ist in dem vorliegenden Buch hervorragend präsent." Ronald Imbihl, Hannover Nachrichten aus der Chemie 6/04 "Den Autoren ist mit "Concepts of Modern Catalysis and Kinetics" ein Werk gelungen, das das Potential zu einem Standardwerk für Katalytiker besitzt. So findet sowohl der Anfänger einen guten Einstieg in das komplexe Thema, als auch für den Experten finden sich zahlreiche neue Aspekte und eine sehr gute Übersicht." Chemie-Online "Als Autoren waren Kenner und Könner am Werk, die die Katalyse von den theoretisch-chemischen und physikalischen-chemischen Grundlagen bis zur Anwendung in der Prozesstechnik gründlich verstanden haben. Jedem, der sich eine solide Grundlage auf dem Gebiet der Katalyse verschaffen möchte, kann dieses Buch ohne Einschränkung empfohlen werden." J. Weikamp, Stuttgart, Chemie Ingenieur Technik, 12/2004 "... ein ansprechendes Buch, das sich sehr gut zur Vorbereitung von Vorlesungen und Seminaren im Grund- und Hauptstudium eignet und eine hochwertige Ergänzung der Katalyse-Literatur abgibt." Paul A. Sermon, Department of Chemistry, University of Surrey, Guildford, Angewandte Chemie, 4. Aprilheft 2004-117/16 + IE 2005-44/16Table of ContentsPreface xiii List of Acronyms xvii 1 Introduction to Catalysis 1 1.1 What Is Catalysis? 2 1.2 Catalysts Can Be Atoms,Molecules, Enzymes, and Solid Surfaces 4 1.2.1 Homogeneous Catalysis 5 1.2.2 Biocatalysis 5 1.2.3 Heterogeneous Catalysis 6 1.3 Why Is Catalysis Important? 9 1.3.1 Catalysis and Green Chemistry 9 1.3.2 Atom Efficiency, E Factors, and Environmental Friendliness 10 1.3.3 The Chemical Industry 11 1.4 Catalysis as a Multidisciplinary Science 16 1.4.1 The Many Length Scales of a “Catalyst” 16 1.4.2 Time Scales in Catalysis 17 1.5 The Scope of this Book 18 1.6 Appendix: Catalysis in Journals 18 References 22 2 Kinetics 23 2.1 Introduction 23 2.2 The Rate Equation and Power Rate Laws 25 2.3 Reactions and Thermodynamic Equilibrium 28 2.3.1 Example of Chemical Equilibrium: The Ammonia Synthesis 31 2.3.2 Chemical Equilibrium for a Nonideal Gas 33 2.4 The Temperature Dependence of the Rate 35 2.5 Integrated Rate Equations: Time Dependence of Concentrations in Reactions of Different Orders 38 2.6 Coupled Reactions in Flow Reactors: The Steady State Approximation 41 2.7 Coupled Reactions in Batch Reactors 45 2.8 Catalytic Reactions 48 2.8.1 The Mean-Field Approximation 52 2.9 Langmuir Adsorption Isotherms 53 2.9.1 Associative Adsorption 53 2.9.2 Dissociative Adsorption 54 2.9.3 Competitive Adsorption 55 2.10 Reaction Mechanisms 55 2.10.1 Langmuir–Hinshelwood or Eley–Rideal Mechanisms 56 2.10.2 Langmuir–Hinshelwood Kinetics 56 2.10.3 The Complete Solution 57 2.10.4 The Steady State Approximation 58 2.10.5 The Quasi-Equilibrium Approximation 59 2.10.6 Steps with Similar Rates 60 2.10.7 Irreversible Step Approximation 61 2.10.8 TheMARI Approximation 61 2.10.9 The Nearly Empty Surface 62 2.10.10 The Reaction Order 63 2.10.11 The Apparent Activation Energy 63 2.11 Entropy, Entropy Production, Auto Catalysis, and Oscillating Reactions 67 2.12 Kinetics of Enzyme-Catalyzed Reactions 73 References 77 3 Reaction Rate Theory 79 3.1 Introduction 79 3.2 The Boltzmann Distribution and the Partition Function 80 3.3 Partition Functions of Atoms andMolecules 83 3.3.1 The Boltzmann Distribution 83 3.3.2 Maxwell–Boltzmann Distribution of Velocities 86 3.3.3 Total Partition Function of a System 87 3.4 Molecules in Equilibrium 93 3.5 Collision Theory 100 3.5.1 Reaction Probability 104 3.5.2 Fundamental Objection against Collision Theory 105 3.6 Activation of Reacting Molecules by Collisions: The Lindemann Theory 106 3.7 Transition State Theory 107 3.8 Transition State Theory of Surface Reactions 113 3.8.1 Adsorption of Atoms 113 3.8.2 Adsorption ofMolecules 118 3.8.3 Reaction between Adsorbates 121 3.8.4 Desorption ofMolecules 123 3.9 Summary 124 References 127 4 Catalyst Characterization 129 4.1 Introduction 129 4.2 X-ray Diffraction (XRD) 131 4.3 X-ray Photoelectron Spectroscopy (XPS) 134 4.4 X-ray Absorption Spectroscopy (EXAFS and XANES) 139 4.4.1 Extended X-ray Absorption Fine Structure (EXAFS) 139 4.4.2 X-ray Absorption Near-Edge Spectroscopy (XANES) 143 4.5 Electron Microscopy 144 4.6 Mossbauer Spectroscopy 148 4.7 Ion Spectroscopy: SIMS, LEIS, RBS 151 4.8 Temperature-Programmed Reduction, Oxidation, and Sulfidation 155 4.9 Infrared Spectroscopy 158 4.10 Surface Science Techniques 160 4.10.1 Low Electron Energy Diffraction (LEED) 161 4.10.2 Scanning ProbeMicroscopy 164 4.11 Concluding Remarks 169 References 170 5 SolidCatalysts 173 5.1 Requirements of a Successful Catalyst 173 5.2 The Structure ofMetals, Oxides, and Sulfides and Their Surfaces 175 5.2.1 Metal Structures 175 5.2.2 Surface Crystallography of Metals 176 5.2.3 Oxides and Sulfides 182 5.2.4 Surface Free Energy 185 5.3 Characteristics of Small Particles and Porous Material 187 5.3.1 The Wulff Construction 187 5.3.2 The Pore System 190 5.3.3 The Surface Area 191 5.4 Catalyst Supports 197 5.4.1 Silica 197 5.4.2 Alumina 199 5.4.3 Carbon 201 5.4.4 Shaping of Catalyst Supports 201 5.5 Preparation of Supported Catalysts 203 5.5.1 Coprecipitation 203 5.5.2 Impregnation, Adsorption, and Ion Exchange 203 5.5.3 Deposition Precipitation 205 5.6 Unsupported Catalysts 206 5.7 Zeolites 206 5.7.1 Structure of a Zeolite 207 5.7.2 Compensating Cations and Acidity 208 5.7.3 Applications of Zeolites 209 5.8 Catalyst Testing 210 5.8.1 Ten Commandments for Testing Catalysts 211 5.8.2 Activity Measurements 213 References 223 6 Surface Reactivity 225 6.1 Introduction 225 6.2 Physisorption 226 6.2.1 The Van derWaals Interaction 226 6.2.2 Including the Repulsive Part 227 6.3 Chemical Bonding 228 6.3.1 Bonding in Molecules 229 6.3.2 The Solid Surface 233 6.4 Chemisorption 246 6.4.1 The Newns–Anderson Model 246 6.4.2 Summary of the Newns–Anderson Approximation in Qualitative Terms 252 6.4.3 Electrostatic Effects in Atomic Adsorbates on Jellium 254 6.5 Important Trends in Surface Reactivity 256 6.5.1 Trend in Atomic Chemisorption Energies 257 6.5.2 Trends in Molecular Chemisorption 261 6.5.3 Trends in Surface Reactivity 265 6.5.4 Universality in Heterogeneous Catalysis 274 6.5.5 Scaling Relations 276 6.5.6 Appendix: Density Functional Theory (DFT) 278 References 280 7 Kinetics of Reactions on Surfaces 283 7.1 Elementary Surface Reactions 283 7.1.1 Adsorption and Sticking 283 7.1.2 Desorption 289 7.1.3 Lateral Interactions in Surface Reactions 295 7.1.4 Dissociation Reactions on Surfaces 297 7.1.5 Intermediates in Surface Reactions 301 7.1.6 Association Reactions 301 7.2 Kinetic Parameters from Fitting Langmuir–Hinshelwood Models 304 7.3 Microkinetic Modeling 306 7.3.1 Reaction Scheme and Rate Expressions 307 7.3.2 Activation Energy and Reaction Orders 310 7.3.3 Ammonia Synthesis Catalyst underWorking Conditions 313 References 315 8 Catalysis in Practice: Synthesis Gas and Hydrogen 319 8.1 Introduction 319 8.2 Synthesis Gas and Hydrogen 319 8.2.1 Steam Reforming: Basic Concepts of the Process 321 8.2.2 Mechanistic Detail of Steam Reforming 323 8.2.3 Challenges in the Steam Reforming Process 326 8.2.4 The SPARG Process: Selective Poisoning by Sulfur 328 8.2.5 Gold–Nickel Alloy Catalyst for Steam Reforming 329 8.2.6 Direct Uses of Methane 330 8.3 Reaction of Synthesis Gas 332 8.3.1 Methanol Synthesis 332 8.3.2 Fischer–Tropsch Process 343 8.4 Water–Gas Shift Reaction 351 8.5 Synthesis of Ammonia 353 8.5.1 History of Ammonia Synthesis 353 8.5.2 Ammonia Synthesis Plant 355 8.5.3 Operating the Reactor 356 8.5.4 Scientific Rationale for Improving Catalysts 359 8.6 Promoters and Inhibitors 361 8.7 The “Hydrogen Society” 364 8.7.1 The Need for Sustainable Energy 364 8.7.2 Sustainable Energy Sources 366 8.7.3 Energy Storage 368 8.7.4 Hydrogen Fuel Cells 377 References 385 9 Oil Refining and Petrochemistry 391 9.1 Crude Oil 391 9.2 Hydrotreating 394 9.2.1 Heteroatoms and Undesired Compounds 395 9.2.2 Hydrotreating Catalysts 397 9.2.3 Hydrodesulfurization Reaction Mechanisms 399 9.3 Gasoline Production 402 9.3.1 Fluidized Catalytic Cracking 404 9.3.2 Reforming and Bifunctional Catalysis 406 9.3.3 Alkylation 410 9.4 Petrochemistry: Reactions of Small Olefins 412 9.4.1 Ethylene Epoxidation 412 9.4.2 Partial Oxidation and Ammoxidation of Propylene 413 9.4.3 Polymerization Catalysis 415 References 418 10 Environmental Catalysis 421 10.1 Introduction 421 10.2 Air Pollution by Automotive Exhaust 422 10.2.1 The Three-Way Catalyst 423 10.2.2 Catalytic Reactions in the Three-Way Catalyst: Mechanism and Kinetics 429 10.2.3 Concluding Remarks on Automotive Catalysts 436 10.3 Air Pollution by Large Stationary Sources 437 10.3.1 Selective Catalytic Reduction: The SCR Process 437 10.3.2 The SCR Process for Mobile Units 443 References 444 Appendix 447 Questions and Exercises 449 Index 497

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Book SynopsisWritten by an excellent, highly experienced and motivated team of lecturers, this textbook is based on one of the most successful courses in catalysis and as such is tried-and-tested by generations of graduate and PhD students, i.e. the Catalysis-An-Integrated-Approach (CAIA) course organized by NIOK, the Dutch Catalysis research school. It covers all essential aspects of this important topic, including homogeneous, heterogeneous and biocatalysis, but also kinetics, catalyst characterization and preparation, reactor design and engineering. The perfect source of information for graduate and PhD students in chemistry and chemical engineering, as well as for scientists wanting to refresh their knowledgeTable of ContentsPreface xiii 1 Introduction 1Leon Lefferts, Ulf Hanefeld, and Harry Bitter 1.1 A FewWords at the Beginning 1 1.2 Catalysis in a Nutshell 1 1.3 History of Catalysis 3 1.3.1 Industrial Catalysis 4 1.3.2 Environmental Catalysis 5 1.4 Integration Homo–Hetero-Biocatalysis 5 1.5 Research in Catalysis 10 1.5.1 S-Curve, Old Processes Improvement Is Knowledge Intensive 10 1.5.2 Interdependence with Other Fields 11 1.5.3 Recent and Future Issues 12 1.6 Catalysis and Integrated Approach or How to Use this Book 14 References 14 2 Heterogeneous Catalysis 15Leon Lefferts, Emiel Hensen, and Hans Niemantsverdriet 2.1 Introduction 15 2.1.1 Concept of Heterogeneous Catalysis 15 2.1.2 Applications of Heterogeneous Catalysis 16 2.1.3 Catalytic Cycle 23 2.2 Adsorption on Surfaces 23 2.2.1 Physisorption and Chemisorption 24 2.2.2 Adsorption Isotherms 26 2.2.3 Chemisorption and Chemical Bonding 28 2.2.4 Connecting Kinetic andThermodynamic Formulations 33 2.3 Surface Reactions 35 2.3.1 Reaction Mechanism and Kinetics 35 2.4 Types of Heterogeneous Catalysts 41 2.4.1 Supported Metals 41 2.4.2 Oxides and Sulfides 51 2.4.3 Solid Acid Catalysts 62 Question 1 69 Question 2 69 References 70 3 Homogeneous Catalysis 73Elisabeth Bouwman,Martin C. Feiters, and Robertus J. M. Klein Gebbink 3.1 Framework and Outline 73 3.1.1 Outline of this Chapter 73 3.1.2 Definitions and Terminology 74 3.2 Coordination and Organometallic Chemistry 75 3.2.1 Coordination Chemistry: d Orbitals, Geometries, Crystal Field Theory 75 3.2.2 σ and π donors and back-donation: CO, alkene, phosphane, H2 77 3.2.3 Organometallics: Hapticity, Metal–Alkyl/Allyl, Agostic Interaction, Carbenes 80 3.2.4 Electron Counting: Ionogenic or Donor-Pair versus Covalent or Neutral-Ligand 81 3.2.5 Effect of Binding on Ligands andMetal Ions, Stabilization of Oxidation States 83 3.3 Elementary Steps in Homogeneous Catalysis 84 3.3.1 Formation of the Active Catalyst Species 84 3.3.2 Oxidative Addition and Reductive Elimination 85 3.3.3 Migration and Elimination 87 3.3.4 Oxidative Coupling and Reductive Cleavage 90 3.3.5 Alkene or Alkyne Metathesis and σ-Bond Metathesis 90 3.3.6 Nucleophilic and Electrophilic Attack 92 3.4 Homogeneous Hydrogenation 95 3.4.1 Background and Scope 95 3.4.2 H2 DihydrideMechanism:Wilkinson’s Catalyst 96 3.4.3 H2 Monohydride Mechanism and Heterolytic Cleavage 97 3.4.4 Asymmetric Homogeneous Hydrogenation 98 3.4.5 Transfer Hydrogenation with 2-Propanol 100 3.4.6 Other Alkene Addition Reactions 102 3.5 Hydroformylation 104 3.5.1 Scope and Importance of the Reaction and Its Products 104 3.5.2 Cobalt-Catalyzed Hydroformylation 105 3.5.3 Rhodium-Catalyzed Hydroformylation 107 3.5.4 Asymmetric Hydroformylation 110 3.6 Oligomerization and Polymerization of Alkenes 112 3.6.1 Scope and Importance of Oligomerization and Polymerization 112 3.6.2 Oligomerization of Ethene (Ni, Cr) 113 3.6.3 Stereochemistry and Mechanism of Propene Polymerization 115 3.6.4 Metallocene Catalysis 117 3.6.5 Polymerization with Non-Metallocenes (Pd, Ni, Fe, Co) 118 3.7 Miscellaneous Homogeneously Catalyzed Reactions 118 3.7.1 Cross-Coupling Reactions: Pd-Catalyzed C–C Bond Formation 118 3.7.2 Metathesis Reactions 120 Question 1 (total 20 points) 122 Question 2 (total 20 points) 122 References 123 Further Reading 124 4 Biocatalysis 127Guzman Torrelo, Frank Hollmann, and Ulf Hanefeld 4.1 Introduction 127 4.2 Why Are Enzymes So Huge? 129 4.3 Classification of Enzymes 137 4.3.1 Oxidoreductases (EC 1) 139 4.3.2 Transferases (EC 2) 147 4.3.3 Hydrolases (EC 3) 147 4.3.4 Lyases (EC 4) 157 4.4 Concepts and Methods 157 4.4.1 Cofactor Regeneration Systems 158 4.4.2 Methods to Shift Unfavorable Equilibria 159 4.4.3 Two-Liquid-Phase Systems (and Related) 164 4.4.4 (Dynamic) Kinetic Resolutions and Desymmetrization 164 4.4.5 Enantiomeric Ratio E 168 4.5 Applications and Case Studies 169 4.5.1 Oxidoreductases (E.C. 1) 169 4.5.2 Transferases (EC 2) 177 4.5.3 Hydrolases (EC 3) 179 4.5.3.1 Lipases and Esterases (EC 3.1.1) 179 4.5.4 Lyases (EC 4) 181 Question 1 186 Question 2 186 Question 3 187 Question 4 188 Further Reading 188 5 Chemical Kinetics of Catalyzed Reactions 191Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis 5.1 Introduction 191 5.2 Rate Expressions – Quasi-Steady-State Approximation and Quasi-Equilibrium Assumption 193 5.3 Adsorption Isotherms 198 5.3.1 One-Component Adsorption 198 5.3.2 Multicomponent Adsorption 199 5.3.3 Dissociative Adsorption 200 5.4 Rate Expressions – Other Models and Generalizations 200 5.5 Limiting Cases – Reactant and Product Concentrations 202 5.6 Temperature and Pressure Dependence 206 5.6.1 Transition-StateTheory 207 5.6.2 Forward Reaction – Temperature and Pressure Dependence 208 5.6.3 Forward Reaction – Limiting Cases 209 5.7 Sabatier Principle – Volcano Plot 213 5.8 Concluding Remarks 214 Notation 216 Greek 217 Subscripts 217 Superscripts 217 Question 1 217 Question 2 218 Question 3 218 References 219 6 Catalytic Reaction Engineering 221Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis 6.1 Introduction 221 6.2 Chemical Reactors 222 6.2.1 Balance and Definitions 222 6.2.2 Batch Reactor 224 6.2.2.1 Multiple Reactions 226 6.2.3 Continuous Flow Stirred Tank Reactor (CSTR) 228 6.2.4 Plug-Flow Reactor (PFR) 231 6.2.5 Comparison between Plug-flow and CSTR reactor 233 6.3 Reaction and Mass Transport 236 6.3.1 External Mass Transfer 237 6.3.2 Internal Mass Transport 242 6.3.3 Gas–Liquid Mass Transfer 248 6.3.4 Heat Transfer 254 6.4 Criteria to Check for Transport Limitations 257 6.4.1 Numerical Checks 257 6.4.2 Experimental Checks 260 Notation 264 Greek symbols 265 Subscripts 265 Question 1 265 Question 2 266 Question 3 267 References 269 7 Characterization of Catalysts 271Guido Mul, Frank de Groot, Barbara Mojet-Mol, and Moniek Tromp 7.1 Introduction 271 7.1.1 Importance of Characterization of Catalysts 271 7.1.2 Overview of the Various Techniques 271 7.2 Techniques Based on Probe Molecules 273 7.2.1 Temperature-Programmed Techniques 273 7.2.2 Physisorption and Chemisorption 275 7.3 Electron Microscopy Techniques 280 7.4 Techniques from Ultraviolet up to Infrared Radiation 283 7.4.1 UV/Vis Spectroscopy 283 7.4.2 Infrared Spectroscopy 286 7.4.3 Raman Spectroscopy 289 7.5 Techniques Based on X-Rays 291 7.5.1 Introduction 291 7.5.2 Interaction of X-Rays with Matter 293 7.5.3 X-Ray Photoelectron Spectroscopy (XPS) 294 7.5.4 X-ray Absorption Spectroscopy (XAS) 295 7.5.5 X-Ray Scattering 299 7.5.6 X-Ray Microscopy 302 7.6 Ion Spectroscopies 303 7.7 Magnetic Resonance Spectroscopy Techniques 304 7.7.1 NMR 304 7.7.2 EPR 306 7.8 Summary 310 Question 1 310 Question 2 311 Question 3 312 References 313 8 Synthesis of Solid Supports and Catalysts 315Petra de Jongh and Krijn de Jong 8.1 Introduction 315 8.2 Support Materials 317 8.2.1 Mesoporous Metal Oxides 318 8.2.2 Ordered Microporous Materials 326 8.2.3 Carbon Materials 331 8.2.4 Shaping 333 8.3 Synthesis of Supported Catalysts 333 8.3.1 Colloidal Synthesis Routes 334 8.3.2 Chemical Vapor Deposition 335 8.3.3 Ion Adsorption 338 8.3.4 Deposition Precipitation 341 8.3.5 Co-Precipitation 345 8.3.6 Impregnation and Drying 349 Question 1 357 Question 2 357 Question 3 358 References 358 Index 361

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Book SynopsisThis book illustrates the broad field of enantioselective catalysis by highlighting a few topics, out of myriads, with the double aim to typify selected synthetic achievements and future challenges. Eleven research groups have highlighted topics of interest in either organo- or organometallic catalysis, related to their own expertise. For mature fields, these short chapters, far from being exhaustive, show updated overviews including major recent advances and disclose a few prospects. Other chapters focus on upcoming topics in enantioselective catalysis, i.e. on classes of reactions or families of catalysts that are expected to provide appealing synthetic tools when suitably mastered. For all these areas, recent studies demonstrate highly promising perspectives.

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Book SynopsisVolume 5 in the Catalysts for Fine Chemical Synthesis series describes new procedures for the regio- and stereo-controlled transformations of compounds involving oxidation or reduction reactions. It describes a wide range of catalysts, including organometallic systems, biocatalysts and biomimetics.Table of ContentsCHAPTER 1: Industrial Catalysts for Regio- or Stereo- selective Oxidations and Reductions. A Review of Key Technologies and Targets. J. Whittall CHAPTER 2: Asymmetric Hydrogenation of Alkenes, Enones, Ene-esters and Ene-Acids 2.1: (S)-2,2'- Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation I. Gergely, C. Hegeds and J. Bakos. 2.2: Synthesis and Application of Phosphinite Oxazoline Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and A. Pfaltz. 2.3: Synthesis and Application of Heterocyclic Phosphine Oxazoline (HetPHOX) Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and P.G. Cozzi. 2.4: (R)-2,2',6,6'- Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-3,3'-bipyridine [(R)-Xyl-P-Phos] as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of a-Dehydroamino Acids J. Wu and A.S.C. Chan. 2.5: (R,R)-2,3-Bis(tert-butylmethylphosphine)quinoxaline (Quinox P*) as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of Prochiral Amino Acid and Amine Derivatives T. Imamoto and A. Koide. 2.6: Rhodium-Catalysed Asymmetric Hydrogenation of Indoles R. Kuwano and M. Sawamura. CHAPTER 3: Asymmetric Reduction of Ketones 3.1: (R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane as a Versatile Ligand for Enantioselective Hydrogenations N. Dubrovina and A. Borner. 3.2: Synthesis of Both Enantiomers of 1-Phenylethanol by Reduction of Acetophenone with Geotrichum candidum IFO 5767 K. Nakamura, M. Fujii and Y. Ida. 3.3: Titanocene-Catalysed Reduction of Ketones in the Presence of Water. A Convenient Procedure for the Synthesis of Alcohols by Free-Radical Chemistry A. Rosales, J.M. Cuerva and J.E. Oltra. 3.4: Xyl-TetraPHEMP: A Highly Efficient Biaryl Ligand in the [Diphosphine RuCl2-diamine]-Catalysed Hydrogenation of Simple Aromatic Ketones P.H. Moran, J.P. Henschke, A. Zanotti-Gerosa and I C. Lennon. 3.5: N-Arenesulfonyl- and N-Alkylsulfamoyl-1,2-diphenylethylenediamine Ligands for Ruthenium-Catalysed Asymmetric Transfer Hydrogenation of Activated Ketones M.S. Stephan and B. Mohar. 3.6: The Synthesis and Application of BrXUPHOS: A Novel Monodentate Phosphorus Ligand for the Asymmetric Hydrogenation of Ketones M. Wills, Y. Xu, G. Docherty and G. Woodward. 3.7: In Situ Formation of Ligand and Catalyst: Application in Ruthenium-Catalysed Enantioselective Reduction of Ketones J. Wettergren and H. Adolfsson. 3.8: SYNPHOS and DIFLUORPHOS as Ligands for Ruthenium-Catalysed Hydrogenation of Alkenes and Ketones S. Jeulin, V. Ratovelomanana-Vidal and J-P. Genet. 3.9: An Arene Ruthenium Complex with Polymerizable Side-chains for the Synthesis of Immobilised Catalysts E. Burri, S.B. Wendicke, K. Severin. 3.10: Selective Reduction of Carbonyl Group in beta, gamma- Unsaturated alpha- Ketoesters by Transfer Hydrogenation with Ru-(para-cymene) (TsDPEN) M. Guo, D. Li, Y. Sun and Z. Zhang. 3.11: Preparation of Polymer-Supported Ru-TsDPEN Catalysts and their Use for the Enantioselective Synthesis of (S)-Fluoxetine L. Chai, Y. Li and Q. Wang. 3.12: Polymer-Supported Chiral Sulfonamide-Catalysed Reduction of B-Keto Nitrile: a Practical Synthesis of (R)-Fluoxetine G.Wang and G. Zhao. CHAPTER 4: Imine Reduction and Reductive Amination 4.1: Metal-Free Reduction of Imines: Enantioselective Bronsted Acid-Catalysed Transfer Hydrogenation using Chiral BINOL-Phosphates as Catalysts M. Rueping, E. Sugiono, C. Azap and T. Theissmann. 4.2: Metal-Free Bronsted Acid-Catalysed Transfer Hydrogenation: Enantioselective Synthesis of Tetrahydroquinolines M. Rueping , T. Theissmann and A. P. Antonchick. 4.3: A Highly Stereoselective Synthesis of 3a-Amino-23,24-bisnor-5a-cholane via Reductive Amination S. N. Khan, N.J. Cho and H-S. Kim. CHAPTER 5: Oxidation of Primary and Secondary Alcohols 5.1: Copper (II)-Catalysed Oxidation of Primary Alcohols to Aldehydes with Atmospheric Oxygen S. Jammi and T. Punniyamurthy. 5.2: Solvent-free Dehydrogenation of Secondary Alcohols in the Absence of Hydrogen Abstractors using Robinson's Catalyst G.B.W.L. Ligthart, R.H. Meijer, J. v. Buijtenen, J. Meuldijk, J.A.J.M. Vekemans and L. A. Hulshof. 5.3: 2-Iodoxybenzoic Acid (IBX)/ n-Bu4NBr/ CH2Cl2-H2O: a Mild System for the Selective Oxidation of Secondary Alcohols K. Kittigowittana, M. Pohmakotr, V. Reutrakul and C. Kuhakarn. CHAPTER 6: Hydroxylation, Epoxidation and Related Reactions 6.1: Proline-Catalysed a-Aminoxylation of Aldehydes and Ketones Y. Hayashi and M. Shoji. 6.2: Ru/ Silica* Cat* TEMPO(c)-Mediated Oxidation of Alkenes to a-Hydroxyacids R. Ciriminna and M. Pagliaro. 6.3: Catalytic Enantioselective Epoxidation of trans-Disubstituted and Trisubstituted Alkenes with Arabinose-Derived Ulose T.K. M. Shing, G.Y.C. Leung and T. Luk. 6.4: VO(acac)2/ TBHP-Catalysed Epoxidation of 2-(2-Alkenyl)phenols. Highly Regio- and Diastereo-selective Oxidative Cyclisation to 2,3-Dihydrobenzofuranols and 3-Chromanols A. Lattanzi and A. Scettri. 6.5: An Oxalolidinone Ketone Catalyst for the Asymmetric Epoxidation of cis-Olefins D. Goeddel and Y. Shi. 6.6: a-Fluorotropinone Immobilised on Silica: a New Stereoselective Heterogeneous Catalyst for Epoxidation of Alkenes with Oxone G. Sartori, A. Armstrong, R. Maggi, A. Mazzacani, R. Sartorio, F. Bigi and B. Dominguez-Fernandez. 6.7: Asymmetric Epoxidation Catalysed by Novel Azacrown Ether-Type Chiral Quaternary Ammonium Salts under Phase-Transfer Catalytic Conditions K. Hori, K. Tani, and Y. Tohda. 6.8: Enantioselective Epoxidation of Olefins using Phase-Transfer Conditions and [6-N-((S)-1,2,2-Trimethylpropyl)-5H-dibenz[c,e]azepinium] [rac-TRISPHAT] Salt as Catalyst J. Vachon, C. Perollier, A. Martinez and J. Lacour. 6.9: Catalytic Asymmetric Epoxidation of a,Unsaturated Esters Promoted by a Yttrium-Biphenyldiol Complex M. Shibasaki, H. Kakei and S. Matsunaga.. 6.10: Catalytic Enantioselective Epoxidation of a, -Enones with a BINOL-Zinc Complex A. Minatti and K.H. Dotz 6.11: Asymmetric Epoxidation of Phenyl 2-(3'-Pyridylvinyl) Sulfone using Polyleucine/ Hydrogen Peroxide Gel M. Pitts and J. Whittall. CHAPTER 7: Oxidation of Ketones to Lactones or Enones 7.1: Synthesis of 2-(Phosphinophenyl)pyridine Ligand and its Application to Palladium-Catalysed Asymmetric Baeyer- Villiger Oxidation of Prochiral Cyclobutanones K. Ito and T. Katsuki. 7.2: (D)-Codeinone from (D)-Dihydrocodeinone via the Use of Modified o-Iodoxybenzoic Acid (IBX) P. Mather and J. Whittall. CHAPTER 8: Oxidative C-C Coupling 8.1: Enantioselective Oxidative Coupling of 2-Naphthols Catalysed by a Novel Chiral Vanadium Complex N-S. Xie, Q-Z. Liu, Z-B. Luo, L-Z. Gong, A-Q. Mi and Y-Z. Jiang. 8.2: Catalytic Oxidative Cross-Coupling Reaction of 2-Naphthol Derivatives S. Habaue and T. Temma. 8.3: Oxidative Coupling of Benzene with a,-Unsaturated Aldehydes by Pd(OAc)2/ HPMoV/ O2 System T. Yamada, S. Sakaguchi and Y. Ishii. CHAPTER 9: Oxidation of Sulfides and Sulfoxides 9.1: The First Example of Direct Oxidation of Sulfides to Sulfones by an Osmate- Molecular Oxygen System B.M. Choudary, C. Reddy, V. Reddy, B.V. Prakash, M.L. Kantam and B. Sreedhar. 9.2: Selective Oxidation of Sulfides to Sulfoxides and Sulfones using Hydrogen Peroxide (H2O2) in the Presence of Zirconium Tetrachloride K. Bahrami. 9.3: WO3-30% H2O2-Cinchona Alkaloids: a New Heterogeneous Catalytic System for Asymmetric Oxidation and Kinetic Resolution of Racemic Sulfoxides V. V. Thakur and A. Sudalai. 9.4: Benzyl-4,6-isopropylidene-a-(D)-glucopyranoside, 2-deoxy-2-[[(2-hydroxy-3,5-di-tert-butylphenyl)methylene]amine] as a Ligand for Vanadium-Catalysed Asymmetric Oxidation of Sulfides R. Del Litto, G. Roviello and F. Ruffo. 9.5: Asymmetric Sulfoxidation of Aryl Methyl Sulfides with H2O2 in Water A. Scarso and G. Strukul

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Book SynopsisOver the last 60 years the increasing knowledge of transition metal chemistry has resulted in an enormous advance of homogeneous catalysis as an essential tool in both academic and industrial fields. Remarkably, phosphorus(III) donor ligands have played an important role in several of the acknowledged catalytic reactions. The positive effects of phosphine ligands in transition metal homogeneous catalysis have contributed largely to the evolution of the field into an indispensable tool in organic synthesis and the industrial production of chemicals. This book aims to address the design and synthesis of a comprehensive compilation of P(III) ligands for homogeneous catalysis. It not only focuses on the well-known traditional ligands that have been explored by catalysis researchers, but also includes promising ligand types that have traditionally been ignored mainly because of their challenging synthesis. Topics covered include ligand effects in homogeneous catalysTable of ContentsList of Contributors xv Preface xix 1 Phosphorus Ligand Effects in Homogeneous Catalysis and Rational Catalyst Design 1 Jason A. Gillespie, Erik Zuidema, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer 1.1 Introduction 1 1.2 Properties of phosphorus ligands 7 1.2.1 Electronic ligand parameters 7 1.2.2 Steric ligand parameters 9 1.2.3 Bite angle effects 10 1.2.3.1 Electronic bite angle effect 11 1.2.3.2 Steric bite angle effect 12 1.2.3.3 Steric versus electronic bite angle effects 12 1.2.4 Molecular electrostatic potential (MESP) approach 13 1.3 Asymmetric ligands 15 1.4 Rational ligand design in nickel-catalysed hydrocyanation 19 1.4.1 Introduction 19 1.4.2 Mechanistic insights 20 1.4.3 Rational design 20 1.5 Conclusions 22 References 23 2 Chiral Phosphines and Diphosphines 27 Wei Li and Xumu Zhang 2.1 Introduction 27 2.1.1 Early developments 27 2.2 Chiral chelating diphosphines with a linking scaffold 30 2.2.1 Building chiral backbones from naturally available materials 30 2.2.1.1 Early development 30 2.2.1.2 Syntheses of DIOP variants 31 2.2.1.3 Synthesis from other natural chiral backbones 33 2.2.2 Design and synthesis of chiral backbones 35 2.2.2.1 Chiral backbones synthesized through asymmetric catalysis 35 2.2.2.2 Design and synthesis of ligands containing spiro backbones 37 2.2.2.3 Design and synthesis of chiral ferrocene backbones 40 2.2.2.4 Design and synthesis of other chiral backbones 41 2.2.3 Synthesis from optical resolution of phosphine precursors or intermediates 43 2.3 Chiral atropisomeric biaryl diphosphines 46 2.3.1 Synthesis of BINAP and its derivatives 46 2.3.2 Synthesis of atropisomeric biaryl ligands 49 2.3.3 General strategies of synthesizing of atropisomeric biaryl ligands 52 2.4 Chiral phosphacyclic diphosphines 52 2.4.1 Fundamental discovery and syntheses of BPE and DuPhos 52 2.4.2 Design and synthesis of bisphosphetanes 56 2.4.3 Design and synthesis of bisphospholanes 58 2.4.3.1 BPE and DuPhos analogue ligands 58 2.4.3.2 P-stereogenic bisphospholane ligands 60 2.4.4 Design and synthesis of bisphospholes 63 2.4.5 Design and synthesis of bisphosphinanes 65 2.4.6 Design and synthesis of bisphosphepines 66 2.4.7 Summary of synthetic strategies of phosphacycles 68 2.5 P-stereogenic diphosphine ligands 68 2.6 Experimental procedures for the syntheses of selected diphosphine ligands 69 2.6.1 Synthesis procedure for DIOP* ligand 69 2.6.2 Synthesis procedure of SDP ligands 70 2.6.3 Synthesis procedure of ( R , R )-BICP 71 2.6.4 Synthesis procedure of SEGPHOS 71 2.6.5 Synthesis procedure of Ph-BPE 72 2.6.6 Synthesis procedure of TangPhos 73 2.6.7 Synthesis procedure of Binaphane 74 2.7 Concluding remarks 75 References 75 3 Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis 81 Aitor Gual, Cyril Goddard, Verónica de la Fuente, and Sergio Castillón 3.1 Introduction 81 3.2 Synthesis of phosphites 82 3.2.1 Monophosphites 82 3.2.1.1 Symmetrically substituted monophosphites 82 3.2.1.2 Nonsymmetrically substituted monophosphites 83 3.2.1.3 Caged monophosphites 84 3.2.1.4 Monophosphites bearing dioxaphospho-cyclic units 84 3.2.2 Diphosphite ligands 94 3.2.2.1 Diphosphites not containing a dioxaphospho-cyclic unit 94 3.2.2.2 Diphosphites bearing dioxaphospho-cyclic units 95 3.2.3 Triphosphites 105 3.3 Highlights of catalytic applications of phosphite ligands 106 3.3.1 Hydrogenation reactions 106 3.3.2 Functionalization of alkenes: hydroformylation and hydrocyanation 108 3.3.2.1 Hydroformylation 108 3.3.2.2 Hydrocyanation 110 3.3.3 Addition of nucleophiles to carbonyl compounds and derivatives 110 3.3.3.1 1,2-addition 111 3.3.3.2 1,4-addition 111 3.3.4 Allylic substitution reactions 113 3.3.5 Miscellaneous reactions 117 3.4 General synthetic procedures 122 3.4.1 Symmetrically substituted phosphites 122 3.4.2 Nonsymmetrically substituted phosphites 123 3.4.3 Phosphites bearing dioxaphospho-cyclic units 123 References 124 4 Phosphoramidite Ligands 133 Laurent Lefort and Johannes G. de Vries 4.1 Introduction 133 4.1.1 History 134 4.2 Synthesis of phosphoramidites 134 4.3 Reactivity of the phosphoramidites 135 4.4 Types of phosphoramidite ligands 136 4.4.1 Acyclic monodentate phosphoramidites 136 4.4.2 Cyclic monodentate phosphoramidites based on diols 136 4.4.2.1 Synthesis of binaphthol- and biphenol-based phosphoramidites 137 4.4.2.2 Synthesis of TADDOL-based phosphoramidites 140 4.4.2.3 Synthesis of spiro-based phosphoramidites 141 4.4.2.4 Synthesis of 1,2-diol-based phosphoramidites 141 4.4.2.5 Phosphoramidites based on unusual diols 141 4.4.3 Cyclic phosphoramidites based on amino alcohols 142 4.4.4 Bis-phosphoramidites 143 4.4.4.1 Bis-phosphoramidites based on diamines 143 4.4.4.2 Bis-phosphoramidites based on diols 144 4.4.4.3 Other bidentate phosphoramidites 145 4.4.5 Mixed bidentate ligands 145 4.4.5.1 Phosphoramidite–phosphines 145 4.4.5.2 Phosphoramidite–phosphite 147 4.4.5.3 Phosphoramidite–amines 148 4.4.5.4 Other bidentate phosphoramidite ligands 149 4.4.6 Polydendate phosphoramidites 149 4.5 Conclusion 153 4.6 Synthetic procedures 153 References 153 5 Phosphinite and Phosphonite Ligands 159 T. V. (Babu) RajanBabu 5.1 Introduction 159 5.2 General methods for synthesis of complexes 160 5.3 Syntheses and applications of phosphinite ligands 162 5.3.1 Early studies 162 5.3.2 Phosphinite ligands from carbohydrates 163 5.3.2.1 Rh-catalyzed asymmetric hydrogenation of dehydroaminoacids 164 5.3.2.2 Ni(0)-catalyzed asymmetric hydrocyanation 166 5.3.2.3 Ni(0)- and Pd(0)-catalyzed allylic substitution by carbon nucleophiles 170 5.3.2.4 Rh(I)-catalyzed hydroformylation of vinylarenes 171 5.3.2.5 Ni(II)-catalyzed asymmetric hydrovinylation of alkenes 171 5.3.2.6 Ligands for homogeneous catalysis in water 172 5.3.3 Phosphinite ligands from other alcohols 172 5.3.4 Phosphine–phosphinite and amine–phosphinite ligands 173 5.3.5 Phosphinites from amines, amino alcohols, and amino acids 174 5.3.5.1 Aminophosphines 174 5.3.5.2 Aminophosphine–phosphinite (AMPP) ligands 176 5.3.6 Bisphosphinite ligands with other scaffoldings 179 5.3.7 1,1'-Diaryl-2,2'-phosphinites and dynamic conformational control in asymmetric catalysis 180 5.3.8 Monophosphinite ligands 182 5.3.9 Hybrid ligands containing phosphinites 182 5.3.9.1 Thioether–phosphinite ligands 182 5.3.9.2 Oxazoline–phosphinite and pyridine–phosphinite ligands 184 5.3.9.3 An alkene–phosphinite ligand 186 5.3.9.4 Chiral transition metal Lewis acids bearing electron-withdrawing phosphinites 187 5.4 Synthesis and applications of phosphonite ligands 188 5.4.1 Early studies 188 5.4.2 Phosphonites from TADDOL and related compounds 189 5.4.3 Phosphonites derived from 2,2'-hydroxybiaryls and related compounds 193 5.4.4 Phosphine–phosphonite ligands 196 5.4.5 Phosphonites with paracyclophane backbone 196 5.4.6 Phosphonites with a spirobisindane backbone 197 5.4.7 Miscellaneous phosphonite ligands 198 5.4.8 Development of phosphonite ligands for industrially relevant processes 199 5.4.8.1 Phosphonite ligands in hydroformylation 199 5.4.8.2 Phosphonite ligands in Ni(0)-catalyzed hydrocyanation 201 5.4.8.3 Oxazoline–phosphonite ligands and olefin dimerization 203 5.4.9 Use of the phosphonite functionality to synthesize other ligands 206 5.5 Experimental procedures for the syntheses of prototypical phosphinite and phosphonite ligands 208 5.5.1 Phosphinite ligands 208 5.5.1.1 Me 2 P(OMe) 208 5.5.1.2 Et 2 POEt and EtP(OEt) 2 209 5.5.1.3 Synthesis of methyl 3,4-bis- O -[bis(3,5-dimethylphenyl)phosphino]- 2,6-di- O -benzoyl- a - D -glucopyranoside (Ligand 8) 209 5.5.1.4 Preparation of phenyl 2,3-bis- O -[bis[3,5-bis(trifluoromethyl) phenyl]-phosphino)-4,6- O -benzylidene-glucopyranoside 211 5.5.1.5 Preparation of bis-(pentafluorophenyl)chlorophosphine 212 5.5.1.6 An alternate general procedure for phosphinite incorporation. [(2S,3R)-3-phenylthio-4-methylpent-2-oxy]diphenylphosphine 212 5.5.1.7 Metal-template synthesis of an amino1,2-diarylphosphinediarylphophinite complex 213 5 5.5.1.8 Procedure for the preparation of a bis-aminodiaryphosphine (R)-37 213 5.5.1.9 (-)-(S)-4- tert -butyl-2-{1-di(2'-methylphenyl)phosphinite- 1-methyl-ethyl}-4,5-dihydro-oxazole 214 5.5.1.10 (R)-7-(2-phenyl-6,7-dihydro-5H-[1]pyrindin)-di-(2'-methylphenyl)- phosphinite 215 5.5.2 Phosphonite ligands 217 5.5.2.1 (IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa- 4-phosphabicyclo[5.3.0]-decane 217 5.5.2.2 (IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa- 4-phosphabicyclo/5.3.0]-decane 218 5.5.2.3 Synthesis of (S)-2-[2-(diphenylphosphino)phenyl]-1,3,2-dinaphtho [d1,2,f1,2]dioxaphosphe-pine 219 5.5.2.4 4,5-Bis{di[(2-tert-butyl)phenyl]phosphonito}-9,9-dimethylxanthene 219 5.6 Acknowledgments 221 Abbreviations 221 References 222 6 Mixed Donor Ligands 233 René Tannert and Andreas Pfaltz 6.1 Introduction: general design principles 233 6.2 Synthesis of bidentate P,X-ligands 235 6.2.1 P,N-ligands 235 6.2.1.1 Oxazoline-based P,N-ligands 235 6.2.1.2 Imidazoline-based P,N-ligands 243 6.2.1.3 Oxazole-, thiazole-, and imidazole-based P,N-ligands 243 6.2.1.4 Pyridine-based P,N-ligands 245 6.2.1.5 Amine- and imine-based P,N-ligands 247 6.2.1.6 Other P,N-ligands 250 6.2.2 P,O-ligands 250 6.2.3 P,S-ligands 252 6.2.4 P,C-ligands 255 6.3 Conclusion 257 6.4 Experimental procedures 257 6.4.1 Synthesis of PHOX ligand 257 6.4.2 Synthesis of NeoPHOX ligand 259 References 260 7 Phospholes 267 Duncan Carmichael 7.1 Introduction 267 7.2 Creation of phospholes for use as ligands 269 7.2.1 Reactions of phosphorus dihalides with metallated dienes 269 7.2.2 Reactions of phosphorus dihalides with dienes 270 7.2.3 Michael addition of primary phosphines to dienes 271 7.3 Postsynthetic functionalisation 271 7.3.1 Functionalisation at phosphorus 271 7.3.2 Use of electrophiles 272 7.3.3 Use of nucleophiles and aromatics 272 7.3.4 Elaboration about the phosphole nucleus 272 7.4 Phosphole coordination chemistry 273 7.5 Phospholes in catalysis 276 7.6 Experimental procedures 279 References 280 8 Phosphinine Ligands 287 Christian Müller 8.1 Introduction 287 8.2 Ligand properties 288 8.2.1 Electronic properties 288 8.2.2 Structural characteristics and steric properties 289 8.2.3 Reactivity of phosphinines 290 8.3 Synthesis of Phosphinines 292 8.3.1 O + /P exchange reaction 292 8.3.2 Tin route 294 8.3.3 [4 + 2] cycloaddition reactions 294 8.3.4 Ring expansion methods 295 8.3.5 Metal-mediated functionalizations 296 8.4 Coordination chemistry 297 8.5 Reactivity of transition metal complexes 300 8.6 Application of phosphinines in homogeneous catalysis 300 8.7 Experimental procedure for the synthesis of selected phosphinines 303 References 305 9 Highly Strained Organophosphorus Compounds 309 J. Chris Slootweg 9.1 Introduction 309 9.2 Three-membered rings 310 9.3 Rearrangements 312 9.4 Homogeneous catalysis 313 9.5 Conclusions 314 9.6 Experimental procedures 315 9.6.1 Synthesis of BABAR-Phos 49a (R = i-Pr) 315 9.6.2 Synthesis of BABAR-Phos 49b (R = 3,5-(CF3)2C6H3) 316 References 317 10 Phosphaalkenes 321 Julien Dugal-Tessier, Eamonn D. Conrad, Gregory R. Dake, and Derek P. Gates 10.1 Introduction 321 10.1.1 Frontier molecular orbitals of phosphaalkenes 322 10.2 Synthesis of phosphaalkenes 324 10.2.1 Diphosphinidenecyclobutene (DPCB) synthesis (P,P chelates) 324 10.2.2 Bidentate-chelating P,P phosphaalkene ligands 325 10.2.3 Phosphaalkenes capable of P,N-chelation to metals 326 10.2.4 P,X achiral phosphaalkene ligands (X=P, O, S) 326 10.2.5 Synthesis of enantiomerically pure P,X ligands (X=P, N) 328 10.3 Catalysis with phosphaalkene ligands 329 10.3.1 Ethylene polymerization 329 10.3.2 Cross-coupling reactions 330 10.3.3 Hydro- and dehydrosilylation 332 10.3.4 Hydroamination and hydroamidation 333 10.3.5 Isomerization reactions 334 10.3.6 Allylic substitution 335 10.3.7 Asymmetric catalysis 336 10.4 Concluding remarks 337 10.5 Experimental procedures for representative ligands 338 10.5.1 Synthesis of DPCB 338 10.5.2 Synthesis of PhAk–Ox 338 10.6 Acknowledgments 339 References 339 11 Phosphaalkynes 343 Christopher A. Russell and Nell S. Townsend 11.1 Introduction 343 11.2 General experimental 344 11.3 Preparation of PC t Bu 344 11.3.1 Tris(trimethylsilyl)phosphine, P(SiMe 3 ) 3 345 11.3.2 tert -butylphosphaalkene, Me 3 SiP = C(OSiMe 3 ) t Bu (systematic name [2,2-dimethyl-1-(trimethylsiloxy)propylidene]–(trimethylsilyl) phosphine) 346 11.3.3 (2,2-dimethylpropylidyne)phosphine; t BuC=P 347 11.4 Adamanylphosphaalkyne, AdC=P 348 11.4.1 Adamant-1-yl(trimethylsiloxy)methylidene (trimethylsilyl) phosphane 348 11.4.2 (Adamant-1-ylmethylidyne)phosphane 348 11.5 Mesitylphosphaalkyne, MesC=P 349 11.5.1 Preparation of potassium bis(trimethylsilyl)phosphide {KP(SiMe 3 ) 2 } 349 11.5.2 Mesityl(trimethylsiloxy)methylene trimethylsilylphosphane 349 11.5.3 Mesitylphosphaalkyne 350 11.6 Phospholide anions 350 11.6.1 Preparation of Cp 2 Zr(PC t Bu) 2 351 11.6.2 Preparation of ClP(PC t Bu) 2 351 11.6.3 Preparation of the triphospholide anion and derivation to give the triphenylstannylphosphole 352 11.6.4 Preparation of Cl 3 P 3 (C t Bu) 2 352 11.6.5 Preparation of the triphospholide anion 352 11.7 1,3,5-Triphosphabenzene 352 11.7.1 Preparation of Cl 3 VN t Bu 353 11.7.2 Preparation of 1,3,5-triphospabenzene; P 3 (C t Bu) 3 353 References 353 12 P-chiral Ligands 355 Jérôme Bayardon and Sylvain Jugé 12.1 Introduction 355 12.2 Designing P-chiral ligands using alcohols as chiral auxiliaries 357 12.3 Designing P-chiral ligands using amino alcohols as chiral auxiliaries 363 12.3.1 Synthesis starting from tricoordinated 1,3,2-oxazaphospholidines 363 12.3.2 Synthesis starting from tetracoordinated 1,3,2-oxazaphospholidines 364 12.3.3 Synthesis starting from 1,3,2-oxazaphospholidine borane complexes 366 12.3.3.1 Interest of the borane–phosphorus complex chemistry 366 12.3.3.2 Ephedrine method 366 12.3.3.3 Methyl phosphinite boranes as P-chiral electrophilic building blocks 367 12.3.3.4 Chlorophosphine boranes as P-chiral electrophilic building blocks 368 12.3.3.5 Designing P-chiral aminophosphine phosphinites (AMPP*) 371 12.3.3.6 P-chiral o -hydroxyaryl phosphines 371 12.3.3.7 P-chiral secondary phosphine boranes 373 12.3.3.8 P-chiral 1,2-diphosphinobenzenes 373 12.3.3.9 Strategies for the enantiodivergent synthesis of P-chiral ligands 375 12.4 Designing of P-chiral ligands using amines as chiral auxiliaries 377 12.4.1 Sparteine as chiral auxiliary 377 12.4.2 a -Arylethylamines as chiral auxiliaries 381 12.5 Conclusion 381 12.6 Experimental procedures 383 References 385 13 Phosphatrioxa-Adamantane Ligands 391 Paul G. Pringle and Martin B. Smith 13.1 Introduction 391 13.2 Synthesis of phosphatrioxa-adamantanes 393 13.3 Catalysis supported by phosphatrioxa-adamantane ligands 395 13.3.1 Alkoxycarbonylation 395 13.3.2 Hydroformylation and hydrocyanation 397 13.3.3 Pd-catalysed coupling reactions 399 13.3.4 Asymmetric hydrogenation 400 13.4 Experimental procedures for phosphatrioxa-adamantanes ligands 401 13.4.1 Preparation of CgPH 401 13.4.2 Preparation of CgPH(BH 3 ) 402 13.4.3 Preparation of CgPBr 402 13.4.4 Preparation of CgPCH 2 CH 2 CH 2 PCg (L1) 402 13.4.5 Preparation of CgPPh (L7) 402 References 402 14 Calixarene-based Phosphorus Ligands 405 Angelica Marson, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer 14.1 Introduction 405 14.2 Conformational properties 407 14.3 Calixarene-based phosphorus ligands 409 14.3.1 Phosphines and phosphinites 409 14.3.2 Phosphites and phosphonites 414 14.4 Applications in homogeneous catalysis 422 14.5 Experimental procedures 424 References 425 15 Supramolecular Bidentate Phosphorus Ligands 427 Jarl Ivar van der Vlugt and Joost N. H. Reek 15.1 Introduction: general design principles 427 15.2 Construction of bidentate phosphorus ligands via self-assembly 429 15.2.1 H bonding 429 15.2.2 Metal template assembly 440 15.2.3 Ion templation 445 15.3 Conclusions 446 15.4 Experimental procedures 447 15.4.1 General remarks 447 15.4.2 Synthesis of UREAPhos 447 15.4.3 Synthesis of METAMORPhos 448 15.4.4 Synthesis of supraphos 450 References 459 16 Solid-phase Synthesis of Ligands 463 Michiel C. Samuels, Bert H. G. Swennenhuis, and Paul C. J. Kamer 16.1 Introduction 463 16.2 Insoluble supports in ligand synthesis 466 16.3 Soluble polymeric supports 470 16.4 Supported ligands in catalysis 472 16.5 Solid-phase synthesis of nonsupported ligands 473 16.6 Conclusions and outlook 475 16.7 Experimental procedures 476 References 478 17 Biological Approaches 481 René den Heeten, Paul C. J. Kamer, and Wouter Laan 17.1 Introduction 481 17.2 Peptide-based phosphine ligands 481 17.2.1 Solid-phase synthesis using phosphine-containing amino acids 481 17.2.1.1 Synthesis of phosphine-containing amino acids 482 17.2.1.2 Synthesis and application of phosphine-containing peptides 484 17.2.2 Functionalisation of peptides with phosphines 485 17.2.2.1 Phosphinomethylation of amines 485 17.2.2.2 Phosphine modification of peptides via imine or amide formation 485 17.3 Oligonucleotide-based phosphine ligands 487 17.3.1 Covalent anchoring of phosphines to DNA 487 17.4 Phosphine-based artificial metalloenzymes 488 17.4.1 Supramolecular anchoring of phosphines to proteins 489 17.4.1.1 Avidin–biotin 489 17.4.1.2 Antibodies 490 17.4.2 Covalent anchoring of phosphines 491 17.5 Conclusions and outlook 492 17.6 Representative synthetic procedures 493 17.6.1 Artificial hydrogenases based on the biotin–streptavidin technology 493 17.6.2 Site-selective covalent modification of proteins with phosphines via hydrazone linkage 494 17.7 Acknowledgments 495 References 495 18 The Design of Ligand Systems for Immobilisation in Novel Reaction Media 497 Paul B. Webb and David J. Cole Hamilton 18.1 Introduction 497 18.2 Aqueous biphasic catalysis 499 18.3 Fluorous biphasic catalysis 503 18.4 Ionic liquids as reaction media 507 18.5 Supercritical fluids as solvents in single- and multiphasic reaction systems 512 18.5.1 Biphasic systems based on CO2 516 18.6 Experimental section 518 18.6.1 Trisodium salt of 3,3′,3″-phosphinetriylbenzenesulfonic acid (TPPTS) 518 18.6.2 2,7-bis(SO3Na)-Xantphos 519 18.6.3 Sulfonated BINAP 519 18.6.4 Synthesis of Tris(1H,1H,2H,2H-perfluorooctyl)phosphine 520 18.6.5 Synthesis of Tris (4-tridecafluorohexylphenyl)phosphine 520 18.6.6 (Meta-sulfonatophenyl)diphenylphosphine, sodium salt (monosulfonated triphenylphosphine, TPPMS) 522 18.6.7 1-Propyl-3-methylimidazolium diphenyl(3-sulfonatophenyl)-phosphine ([PrMIM][TPPMS]) 523 18.6.8 4,4′-Phosphorylated 2,2′-Bis(diphenylphosphanyl)-1,1′-binaphthyl 523 18.6.9 Synthesis of (R)-6,6′-bis(perfluorohexyl)-2,2′ bis (diphenylphosphino)-1,1′-binaphthyl ((R)-Rf-BINAP) 524 References 526 Index

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Book SynopsisWritten for senior undergraduate and graduate students, as well as those chemists unfamiliar with “frustrated Lewis pairs (FLPs)”, this text serves as an introduction to the both the concept and application of FLPs in hydrogenation catalysis. The book begins by setting the stage as it was around the turn of the century. While the dramatic impacts of catalysis were undeniable, there was dependence of such technologies on transition metal chemistry. Contrastingly, the chemistry of main group elements was dominated by Lewis acid-base behavior. However, these perceptions were altered with the discovery of the ability of “frustrated Lewis pairs (FLPs)” to activate dihydrogen. The basic features, and mechanisms of action of these unique main group systems are chronicled, while the evolution of the initial findings to applications in catalytic hydrogenation is discussed. A subsequent chapter focuses on the breadth of organic substrates for which borane based FLP hydrogenations are effective. This is furthered with a chapter on the metal-free enantioselective reductions. FLP chemistry is not limited to systems involving boranes and this book also catalogues a range of FLP hydrogenation catalysts involving elements from across the periodic table. The final chapter in the book describes other directions of interest where the application of the concept of FLPs hydrogenation are beginning to emerge. Ideal for course use and self study, this book provides synthetic chemists with a fresh, expert introduction to the field. The reader will be left recognizing that hydrogenation catalysts is a domain no longer limited to transition metals.Table of ContentsContext, Background and Discovery; The Nature of Frustrated Lewis Pairs; Borane-based FLP Hydrogenations; Borane-based Asymmetric Hydrogenations; Structural Variations of FLPs; Other Directions for FLP Hydrogenations

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Book SynopsisEncompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis. The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.Trade ReviewWithout any doubt, this is a very contemporary textbook about catalysis which will definitely be useful for students and post docs, as well as newcomers. It compromises of not only the history and principles of catalysis but in an acceptable manner, it brings together fundamentals and applications of experimental techniques and reaction kinetics together with the design of reactions etc,. I would recommend it to all lecturers and readers not only for catalytic courses but also for other courses in technical and physical chemistry. -- Jiří Čejka, Charles University PragueTable of ContentsHistory of Catalysis; Feedstocks and Renewable Resources; Current Challenges in Catalysis; Organometallic Chemistry and Elementary Steps; Nanoscience; An Introduction to Biocatalysis; Thermodynamics and Kinetics; Heterogeneous Catalysis; Homogenous Catalysis; Organocatalysis; Biocatalysis; Computational Catalysis; Introduction to Electrocatalysis; Photocatalysis; Solid Materials for Heterogeneous Catalysis; Transition Metal Complexes and Ligand Synthesis; Organocatalysts; Enzymes for Biocatalysis: Key Concepts, Engineering Principles and Case Studies; Advanced Solution Spectroscopic Techniques; X-Ray Photoelectron Spectroscopy; Bulk X-Ray Techniques; Adsorption Methods; Temperature Programmed Techniques; Operando Techniques; Reaction and Reactor Engineering; Catalyst Separation; Process Intensification in Catalysis; Transition Metal Catalysed Methanol Carbonylation; Environmental Analyses and Life Cycle Assessment Studies;

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Book SynopsisVisible light is an abundant source of energy. While the conversion of light energy into electrical energy (photovoltaics) is highly developed and commercialized, the use of visible light in chemical synthesis is far less explored. Chemical photocatalysts that mimic principles of biological photosynthesis utilize visible light to drive endothermic or kinetically hindered reactions. This work summarizes in 16 chapters the state of the art and the challenges of this emerging future technology.Table of Contents1. Introduction 2. Giacommo Chiamician, an early pioneer of visible light photochemistry 3. Flavin photocatalysis 4. Templated enantioselective photocatalysis 5. Photocatalysis using DNA and peptides 6. Photoorganoredox catalysis 7. Transition metal catalysis with visible light 8. Theory for the description of excited states in photocatalysis 9. Time resolved 2D spectroscopy analyzing reaction intermediates in photocatalysis 10. Ultrafast spectroscopy in photocatalysis 11. Metal complexes for photohydrogenation and hydrogen evolution 12. Inorganic semiconductors in photocatalysis 13. Photocatalysis with cadmiunsulfid 14. Polyoxometallates in photocatalysis 15. Organic semiconductors in photocatalysis 15. Porphyrin-based photocatalysis 16. Enantioselective chemical photocatalysis Index

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Book SynopsisIn a classical kinetic resolution, two enantiomers of a racemate are transformed into chiral products at different rates with a maximum theoretical yield of 50%. However, the need to reduce costs and waste in synthesis have led to efforts to develop novel resolution procedures proceeding beyond this 50% limited yield. This has led to the evolution of classical kinetic resolution into dynamic kinetic resolution (DKR), allowing a quantitative yield of one of the enantiomers. DKR combines the resolution step of kinetic resolution with an in-situ racemization of the chirally-labile substrate. It is only in the last two decades that chiral green organocatalysts have been demonstrated to be capable of promoting DKRs considerably expanding the synthetic scope of the powerful concept of DKR. Collecting all the developments in the field of DKR, this book shows that a wide variety of organocatalysts allow excellent levels of stereocontrol and yields in many types of transformations. It is a great resource for academics and industrialists interested in green enantioselective catalytic reactions.Table of ContentsIntroduction; Dynamic Kinetic Resolutions Promoted by Cinchona Alkaloid Catalysts; Dynamic Kinetic Resolutions Promoted by Amino Acid Catalysts and Derivatives; Dynamic Kinetic Resolutions Promoted by Phosphoric Acid Catalysts; Dynamic Kinetic Resolutions Promoted by N-Heterocyclic Carbene Catalysts; Dynamic Kinetic Resolutions Promoted by Thiourea Catalysts; Dynamic Kinetic Resolutions Promoted by Pyridine-based Lewis Base Catalysts; Dynamic Kinetic Resolutions Promoted by Tetramizole Catalysts; Dynamic Kinetic Resolutions Promoted by Other Organocatalysts; General Conclusion

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Book SynopsisImplementing biocatalytic strategies in an industrial setting at a commercial scale is a challenging task, necessitating a balance between industrial need against economic viability. With invited contributions from small and large-scale chemical and pharmaceutical companies, this book bridges the gap between academia and industry. Contributors discuss current processes, types of biocatalysts and improvements, industrial motivation and key aspects to economically succeed. With its focus on industry related issues, this book will be a useful tool for future research by both practitioners and academics.Table of ContentsAn Appreciation of Biocatalysis in the Swiss Manufacturing Environment; Biocatalysis - A greener alternative in synthetic chemistry; Biocatalysis synthesis of small molecules – Past, present and future; EntreChem: Building a sustainable business case in biotechnology: from biocatalysis to synthetic biology; Bristol-Myers Squibb: Preparation of chiral intermediates for the development of drugs and API's; Johnson Matthey: A technology provider perspective to biocatalysis in the fine chemicals industry; EnzymeWorks: Recent advance in enzyme engineering for chemical synthesis; Almac: Scalable reduction and oxidation catalysis using ene-reductase enzymes; GSK: Biocatalyst discovery and optimization; PETROBRAS: Efforts on biocatalysis for fuels and chemicals production; Metgen: Value from Wood – Enzymatic Solutions; LentiKat’s: Industrial Biotechnology, Experiences and Visions; EnginZyme: Universal Enzyme Immobilization; Cross-linked Enzyme Aggregates (CLEAs): from Concept to Industrial Biocatalyst; SynBiocat: Protein purification, immobilization and continuous-flow processes; Microvi: MicroNiche EngineeringTM for Biocatalysis in the Water and Chemical Industries; Nofima: Peptide recovery and commercialization by enzymatic hydrolysis of marine biomass; CO2 Solutions: A biomimetic approach to mitigate CO2 Emissions – The use of Carbonic Anhydrase in an "Industrial Lung"

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Book SynopsisCatalysis remains a key technology in a huge number of industrial processes in the 21st century. The catalytic properties of precious metals such as platinum and palladium are well understood. However, these metals are expensive and their supply is limited. Earth-abundant elements such as iron and nickel are, as the name suggests, in plentiful supply and much cheaper to use, but research on their use in catalysis has, historically, lagged behind. As researchers and companies increasingly look for ways to reduce costs and improve the sustainability of their processes there has been a renewed interest in these earth-abundant elements. This book presents a detailed overview of current research on the catalytic uses of the most Earth-abundant elements. Highlighting the top ten most Earth-abundant elements and their various roles in modern synthetic chemistry: s-block metals (Na, K, Mg, Ca), first-row transition metals (Ti, Mn, Fe), and p-block elements (Al, Si, P). The significant stoichiometric use of these elements, and their use as acid, base, dual, and/or redox catalysts will be discussed. It will be of use to industrial and academic researchers as well as graduate students with an interest in catalysis and sustainability.Table of ContentsNa (including catalysis); K (including catalysis); Mg (stoichiometric use); Mg/Ca (catalysis) ; Mg/Ca (asymmetric catalysis); Ti (including catalysis); Mn (catalysis I); Mn (catalysis II); Fe (mechanistic studies); Fe (catalysis); Al (including catalysis); Si (stoichiometric use); Si (catalytic intermediates); P (acid catalysis); P (base catalysis)

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Book SynopsisThis volume brings together the work of both theoreticians and experimentalists on the synthesis of nanoparticles and their use in catalytic reactions. Heterogeneous catalysis is a core area of contemporary physical chemistry posing major fundamental and conceptual challenges, and nanoparticles are ubiquitous in many heterogeneous catalysts, therefore it is now opportune to focus a Faraday Discussion on key aspects of their synthesis, characterisation and use. This Faraday Discussion will explore the modern methods being used to design, synthesise and characterize nanoparticles and how these bridge across the disciplines of physical science and chemical engineering. The core aim of this discussion meeting is to develop a fundamental understanding of these crucial aspects of catalytic science, especially relating to nanoparticle synthesis and use in catalytic reactions, knowledge of which is essential for the design of new catalysts.Table of ContentsControl of Catalytic Nanoparticle Synthesis; The Challenges of Characterising Nanoparticulate Catalyts; Theory as a driving force to understand reactions on nanoparticles; Application of new nanoparticle structures as catalysts

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Book SynopsisNanoparticles exhibit a range of different properties when compared to bulk materials. Their high surface-area to volume ratio makes them particularly attractive for use as catalysts and recent years have seen an explosion of research in this area. The ability to fine-tune the size and structure of nanoparticles means that it is possible to design catalytic materials for improved activity or specificity. As catalysis is one of the key technologies for more sustainable production of both chemicals and energy, the past few years have seen increasing numbers of nanomaterials reported for these applications. Depending on the application, a number of different catalyst synthesis and optimization protocols can be used. This book provides comprehensive links between the design and fabrication method for nanoparticles and their catalytic performance (activity, selectivity and stability) in various applications. Presenting an introduction to the concept of catalyst design and recent developments in the preparation and characterisation of nanomaterials, followed by several chapters on the design of catalysts for specific applications, this book is a valuable resource for researchers working on catalytic reactions, industrial processes and nanomaterial applications.Table of ContentsIntroduction to Nanocatalysts; Characterization of Nanoparticles: Advances; Support Morphology-dependent Activity of Nanocatalysts; Design of Metal-modified Zeolites and Mesoporous Aluminosilicates and Application in the Synthesis of Fine Chemicals; Metal–Organic-framework Nanoparticles: Synthesis, Characterization and Catalytic Applications; Design of Metal-free Nanocatalysts; Nanoparticle Design for the Catalytic Valorization of Lignocellulosic Biomass; Nanocatalysts for CO2 Conversion; Nanoparticles and Nanocomposites Design in Photocatalysis; Nanoparticles in the Water–Gas Shift Reaction and Steam Reforming Reactions; Plasmonic Photocatalysts for Environmental Applications; Nanoparticles-based Electrochemical Sensors and Biosensors

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Book SynopsisThe chemistry that occurs within confined spaces is the product of a collection of forces, often beyond the molecule, and is not easily ascribed to singular factors. There is a breadth of material types that can define a confined space (e.g. macrocycles, interlocked molecules, porous and non-porous crystals, organic and inorganic/coordination cages) which are rarely discussed together. Studies of supramolecular entities in the solution and solid states are also not often compared in the same discussion, even though the concepts are often similar or can be easily transferred between the two. Chapters in this book combine classical host-guest chemistry with catalysis, reactivity, and modern supramolecular chemistry. They cover the many different technologies used to describe and understand reactivity in confined spaces in one accessible title. With contributions from leading experts, Reactivity in Confined Spaces will be relevant for graduate students and researchers working in supramolecular chemistry, both organic- and inorganic-based, homogeneous and heterogeneous catalysis, polymer chemistry, and materials science in general.Table of ContentsMacrocycles, Catenanes and Rotaxanes; Catalytic Strategies Within the Confined Spaces of Coordination Cages; Light-induced Processes in Coordination Cages; Stabilising Reactive Intermediates in Cages; Reactivity in a Self-assembled Organic Host; Properties and Reactivities of Metal Complexes Within Organic Nanocontainers; Catalysis at the Confined Interface of Supramolecular Gels; Catalysis in Confined Space: Relationship Between Metal–Organic Frameworks and Discrete Coordination Cages; Solid/Gas Reactivity of Organometallic Species in Confined Spaces; Topochemistry Meets Supramolecular Chemistry: Opportunities for Targeted Organic Synthesis in Molecular Crystals; Stabilising and Characterising Homogeneous Catalysts in MOFs; Biomimetic Metal–Organic Frameworks: Construction and Catalytic Performance; Catalytic Nanoparticles in Metal–Organic Frameworks; Atomically Precise Metal Clusters in Confined Spaces of Metal–Organic Frameworks

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