Bridging Heterogeneous and Homogeneous Catalysis: Concepts, Strategies, and Applications

There are two main disciplines in catalysis research –– homogeneous and heterogeneous catalysis. This is due to the fact that the catalyst is either in the same phase (homogeneous catalysis) as the reaction being catalyzed or in a different phase (heterogeneous catalysis). Over the past decade, various approaches have been implemented to combine the advantages of homogeneous catalysis (efficiency, selectivity) with those of heterogeneous catalysis (stability, recovery) by the heterogenization of homogeneous catalysts or by carrying out homogeneous reactions under heterogeneous conditions. This unique handbook fills the gap in the market for an up–to–date work that links both homogeneous catalysis applied to organic reactions and catalytic reactions on surfaces of heterogeneous catalysts. As such, it highlights structural analogies and shows mechanistic parallels between the two, while additionally presenting kinetic analysis methods and models that either work for both homogeneous and heterogeneous catalysis. Chapters cover asymmetric, emulsion, phase–transfer, supported homogeneous, and organocatalysis, as well as in nanoreactors and for specific applications, catalytic reactions in ionic liquids, fluorous and supercritical solvents and in water. Finally, the text includes computational methods for investigating structure–reactivity relations. With its wealth of information, this invaluable reference provides academic and industrial chemists with novel concepts for innovative catalysis research.

Preface XV List of Contributors XIX 1 Acid–Base Cooperative Catalysis for Organic Reactions by Designed Solid Surfaces with Organofunctional Groups 1 Ken Motokura, Toshihide Baba, and Yasuhiro Iwasawa 1.1 Introduction 1 1.2 Bifunctional Catalysts Possessing Both Acidic and Basic Organic Groups 2 1.2.1 Urea–Amine Bifunctional Catalyst 2 1.2.2 Sulfonic or Carboxylic Acid–Amine Bifunctional Catalyst 3 1.3 Bifunctional Catalysts Possessing Basic Organic Groups and Acid Sites Derived from Their Support Surface 7 1.3.1 Organic Base–Catalyzed Reactions Enhanced by SiO2 7 1.3.2 Amine–Catalyzed Reactions Enhanced by Acid Site on Silica–Alumina 11 1.3.3 Control of Acid–Base Interaction on Solid Surface 13 1.3.4 Cooperative Catalysis of Acid Site, Primary Amine, and Tertiary Amine 18 1.4 Prospect 19 References 20 2 Catalytic Reactions in or by Room–Temperature Ionic Liquids: Bridging the Gap between Homogeneous and Heterogeneous Catalysis 21 Youquan Deng, Feng Shi, and Qinghua Zhang 2.1 Introduction and Background 21 2.2 Catalysis with IL–Supported or Mediated Metal Nanoparticles 22 2.2.1 Preparation of MNPs in ILs 23 2.2.1.1 IL Itself as the Reducing Agent 24 2.2.1.2 Molecular Hydrogen as Reducing Agent 24 2.2.1.3 NaBH4 as the Reducing Agent 26 2.2.1.4 Other Reducing Agents 27 2.2.2 Characterization of IL–Supported or Mediated MNPs 28 2.2.2.1 XPS and NMR 28 2.2.2.2 SEM and TEM 29 2.2.2.3 Molecular Dynamics Simulations 30 2.2.3 Hydrogenation Reactions 31 2.2.4 IL–Supported Pd NPs 32 2.2.5 IL–Supported Pt and Ir NPs 36 2.2.6 IL–Supported Ru NPs 37 2.2.6.1 IL–Supported Rh NPs 40 2.2.7 C–C Coupling Reactions 42 2.2.7.1 Suzuki Reaction 42 2.2.7.2 Mizoroki–Heck Reaction 45 2.2.7.3 Stille Reaction 47 2.2.7.4 Sonogashira Reaction 48 2.2.7.5 Ullmann Reaction 48 2.2.8 Brief Summary 49 2.3 Reactions Catalyzed by Solid–Supported IL: Heterogeneous Catalysis with Homogeneous Performance 50 2.3.1 Introduction 50 2.3.1.1 Design, Preparation, and Properties of Supported IL–Phase Catalysis 51 2.3.2 Design, Preparation, and Properties of Silica Gel–Confined IL Catalysts 55 2.3.2.1 Design, Preparation, and Properties of Covalently Supported IL Catalysts 56 2.3.3 Catalytic Reaction with Supported IL Catalysts 57 2.3.3.1 Catalytic Hydrogenation 57 2.3.3.2 Selective Oxidation 61 2.3.3.3 Catalytic Carbonylation Reaction 63 2.3.3.4 Water–Gas Shift Reaction 70 2.3.3.5 Isomerization and Oligomerization 72 2.3.3.6 Alkylation and Esterification Reactions 73 2.3.3.7 Asymmetric Catalysis 74 2.3.3.8 Enzyme Catalysis 77 2.3.4 Brief Summary 79 2.4 Outlook 80 References 80 3 Heterogeneous Catalysis with Organic–Inorganic Hybrid Materials 85 Sang–Eon Park and Eun–Young Jeong 3.1 Introduction 85 3.1.1 Ordered Mesoporous Silica 85 3.1.2 Organic–Inorganic Hybrid Materials 88 3.1.3 Heterogeneous Catalysis 89 3.2 Organic–Inorganic Hybrid Materials 91 3.2.1 General Advantages of Organic–Inorganic Hybrid Materials 91 3.2.2 Grafting and Co–Condensation 91 3.2.2.1 Amine Groups 91 3.2.2.2 Ionic Liquids (ILs) 93 3.2.2.3 Others 95 3.2.3 Periodic Mesoporous Organosilicas (PMOs) 96 3.2.3.1 Synthesis of PMOs with Surfactants 96 3.2.3.2 Aliphatic PMO 97 3.2.3.3 Aromatic PMO 98 3.2.3.4 Hybrid Periodic Mesoporous Organosilica (HPMO) 98 3.3 Catalysis of Organic–Inorganic Hybrid Materials 99 3.3.1 Catalytic Application of Organic–Functionalized Mesoporous Silica by Grafting and Co–Condensation Method 99 3.3.1.1 Knoevenagel Condensation 99 3.3.1.2 Aldol Condensation 99 3.3.1.3 Esterification of Alcohol 103 3.3.2 Catalytic Application of Periodic Mesoporous Organosilica 104 3.3.3 Chiral Catalysis 105 3.3.4 Photocatalysis 106 3.4 Summary and Conclusion 107 References 108 4 Homogeneous Asymmetric Catalysis Using Immobilized Chiral Catalysts 111 Lei Wu, Ji Liu, Baode Ma, and Qing–Hua Fan 4.1 Introduction 111 4.2 Soluble Polymeric Supports and Catalyst Separation Methods 112 4.2.1 Types of Soluble Polymeric Supports 112 4.2.2 Immobilized Catalyst Separation Methods 114 4.3 Chiral Linear Polymeric Catalysts 114 4.4 Chiral Dendritic Catalysts 126 4.5 Helical Polymeric Catalysts 139 4.6 Conclusion and Prospects 143 Acknowledgments 146 References 146 5 Endeavors to Bridge the Gap between Homo– and Heterogeneous Asymmetric Catalysis with Organometallics 149 Xingwang Wang, Zheng Wang, and Kuiling Ding 5.1 General Introduction 149 5.2 Combinatorial Approach for Homogeneous Asymmetric Catalysis 151 5.2.1 The Principle of Combinatorial Approach to Chiral Catalyst Discovery 152 5.2.2 Ti(IV)–Catalyzed Enantioselective Reactions 153 5.2.2.1 Schiff Base/Ti(IV)–Catalyzed Asymmetric Hetero–Diels–Alder Reaction 153 5.2.2.2 BINOLate/Ti(IV)–Catalyzed Asymmetric Hetero–Diels–Alder Reaction 154 5.2.2.3 BINOLate/Ti–Catalyzed Asymmetric Carbonyl–Ene Reaction 156 5.2.2.4 BINOLate/Ti–Catalyzed Asymmetric Ring–Opening Aminolysis of Epoxides 158 5.2.3 Zn Complex–Catalyzed Enantioselective Reactions 159 5.2.3.1 Chiral Amino Alcohol/Zn/Racemic Amino Alcohol–Catalyzed Asymmetric Diethylzinc Addition to Aldehydes 159 5.2.3.2 BINOLate/Zn/Diimine–Catalyzed Asymmetric Diethylzinc Addition to Aldehydes 162 5.2.3.3 BINOLate/Zn/Diimine–Catalyzed Asymmetric Hetero–Diels–Alder Reaction 165 5.2.4 Ru Complex–Catalyzed Enantioselective Reactions 168 5.2.4.1 Achiral Monophosphine/Ru/Chiral Diamine–Catalyzed Asymmetric Hydrogenation of Ketones 168 5.2.4.2 Achiral Bisphosphine/Ru/Chiral Diamine–Catalyzed Asymmetric Hydrogenation of Ketones 171 5.3 Self–Supporting Approach for Heterogeneous Asymmetric Catalysis 172 5.3.1 The Principle of Design and Generation of Self–Supported Catalysts 175 5.3.2 Self–Supported BINOLate/Ti(IV)–Catalyzed Asymmetric Carbonyl–Ene Reaction 178 5.3.3 Self–Supported BINOLate/Ti(IV)–Catalyzed Asymmetric Sulfoxidation Reaction 178 5.3.4 Self–Supported BINOLate/La(III)–Catalyzed Asymmetric Epoxidation 180 5.3.5 Self–Supported BINOLate/Zn(II)–Catalyzed Asymmetric Epoxidation 183 5.3.6 Self–Supported Noyori–Type Ru(II)–Catalyzed Asymmetric Hydrogenation 185 5.3.7 Self–Supported MonoPhos/Rh(I)–Catalyzed Asymmetric Hydrogenation Reactions 187 5.3.7.1 Covalent Bonded Bridging Ligands for Self–Supported Catalysts 187 5.3.7.2 Hydrogen–Bonded Bridging Ligands for Self–Supported Catalysts 190 5.3.7.3 Metal–Coordinated Bridging Ligands for Self–Supported Catalysts 192 5.4 Conclusions and Outlook 194 Acknowledgments 195 References 195 6 Catalysis in and on Water 201 Shifang Liu and Jianliang Xiao 6.1 Introduction 201 6.2 Catalytic Reactions in and ‘‘on’’ Water 202 6.2.1 Hydroformylation 202 6.2.2 Hydrogenation 208 6.2.2.1 Achiral Hydrogenation 209 6.2.2.2 Asymmetric Hydrogenation 215 6.2.3 C–C Bond Formation 220 6.2.3.1 Diels–Alder Reaction 220 6.2.3.2 Friedel–Crafts Reaction 224 6.2.3.3 Suzuki–Miyaura Coupling 226 6.2.3.4 Heck Reaction 234 6.2.3.5 Alcohol Oxidation 238 6.3 Conclusions 244 References 244 7 A Green Chemistry Strategy: Fluorous Catalysis 253 Zhong–Xing Jiang, Xuefei Li, and Feng–Ling Qing 7.1 History of Fluorous Chemistry 253 7.2 Basics of Fluorous Chemistry 254 7.3 Fluorous Metallic Catalysis 263 7.3.1 Fluorous Palladacycle Catalysts 264 7.3.2 Fluorous Pincer Ligand–Based Catalysts 265 7.3.3 Fluorous Immobilized Nanoparticles Catalysts 267 7.3.4 Fluorous Palladium–NHC Complexes 270 7.3.5 Fluorous Phosphine–Based Palladium Catalyst 271 7.3.6 Fluorous Grubbs’ Catalysts 272 7.3.7 Fluorous Silver Catalyst 273 7.3.8 Fluorous Wilkinson Catalyst 273 7.3.9 Miscellaneous Fluorous Catalysts 274 7.4 Fluorous Organocatalysis 275 7.4.1 Asymmetric Aldol Reaction 276 7.4.2 Morita–Baylis–Hillman Reaction 277 7.4.3 Asymmetric Michael Addition Reaction 278 7.4.4 Catalytic Oxidation Reaction 278 7.4.5 Catalytic Acetalization Reaction 279 7.4.6 Catalytic Condensation Reaction 279 7.4.7 Catalytic Asymmetric Fluorination Reaction 280 7.5 Conclusion 281 References 281 8 Emulsion Catalysis: Interface between Homogeneous and Heterogeneous Catalysis 283 Yan Liu, Zongxuan Jiang, and Can Li 8.1 Introduction 283 8.1.1 Water in Chemistry 283 8.1.2 Water as Solvent 283 8.1.3 Emulsion 285 8.1.4 Emulsion Catalysis 285 8.2 Emulsion Catalysis in the Oxidative Desulfurization 287 8.2.1 Emulsion Catalytic Oxidative Desulfurization Using H2O2 as Oxidant 287 8.2.2 Emulsion Catalytic Oxidative Desulfurization Using O2 as Oxidant 296 8.3 Emulsion Catalysis in Lewis Acid–Catalyzed Organic Reactions 297 8.4 Emulsion Catalysis in Reactions with Organocatalysts 303 8.4.1 Aldol Reaction 303 8.4.2 Michael Addition 309 8.5 Emulsion Formed with Polymer–Bounded Catalysts 312 8.5.1 Emulsion Catalysis Participated by Metal Nanoparticles Stabilized by Polymer 312 8.5.2 Polymer–Bounded Organometallic Catalysts in Emulsion Catalysis 315 8.6 Conclusion and Perspective 319 References 320 9 Identification of Binding and Reactive Sites in Metal Cluster Catalysts: Homogeneous–Heterogeneous Bridges 325 Michael M. Nigra and Alexander Katz 9.1 Introduction 325 9.2 Control of Binding in Metal–Carbonyl Clusters via Ligand Effects 332 9.3 Imaging of CO Binding on Noble Metal Clusters 337 9.4 Imaging of Open Sites in Metal Cluster Catalysis 339 9.5 Elucidating Kinetic Contributions of Open Sites: Kinetic Poisoning Experiments Using Organic Ligands 340 9.6 More Approaches to Poisoning Open Catalytic Active Sites to Obtain Structure Function Relationships 343 9.6.1 Using Atomic Layer Deposition of Al2O3 to Block Sites on Pd/Al2O3 Catalysts 343 9.6.2 Bromide Poisoning of Active Sites on Au/TiO2 Catalysts for CO Oxidation Reactions 344 9.6.3 Bromide Poisoning of Active Sites on Au/TiO2 Catalysts for Water–Gas Shift Reactions 345 9.7 Supported Molecular Iridium Clusters for Ethylene Hydrogenation 346 9.8 Summary and Outlook 348 References 349 10 Catalysis in Porous–Material–Based Nanoreactors: a Bridge between Homogeneous and Heterogeneous Catalysis 351 Qihua Yang and Can Li 10.1 Introduction 351 10.2 Preparation of Nanoreactors Based on Porous Materials 352 10.2.1 Mesoporous Silicas 353 10.2.2 Metal–Organic Frameworks (MOFs) 354 10.2.3 Surface Modification of Nanoreactors 355 10.2.3.1 Surface Modification of Mesoporous Silicas (MSs) 355 10.2.3.2 Surface Modification of MOFs 358 10.3 Assembly of the Molecular Catalysts in Nanoreactors 359 10.3.1 Incorporating Chiral Molecular Catalysts in Nanoreactors through Covalent–Bonding Methods 359 10.3.2 Immobilizing Chiral Molecular Catalysts in Nanoreactors through Noncovalent Bonding Methods 363 10.3.2.1 Introduction of Molecular Catalysts into Nanoreactors through Noncovalent Bonding Methods 363 10.3.2.2 Encapsulating Molecular Catalyst in Nanoreactors by Reducing the Pore Entrance Size 366 10.4 Catalytic Reactions in Nanoreactors 369 10.4.1 Pore Confinement Effect 369 10.4.2 Enhanced Cooperative Activation Effect in Nanoreactors 377 10.4.2.1 The Kinetic Resolution of Epoxides 377 10.4.2.2 Water Oxidation Reactions 380 10.4.2.3 Epoxide Hydration 381 10.4.3 Isolation Effect in Nanoreactors 382 10.4.3.1 Selectivity Control 382 10.4.3.2 Inhibiting Dimerization of Molecular Catalysts 385 10.4.4 Microenvironment Engineering of Nanoreactors 385 10.4.5 Influence of the Porous Structure on the Catalytic Performance of Nanoreactors 388 10.4.6 Catalytic Nanoreactor Engineering 390 10.5 Conclusions and Perspectives 390 References 392 11 Heterogeneous Catalysis by Gold Clusters 397 Jiahui Huang and Masatake Haruta 11.1 Introduction 397 11.2 Preparation of Gold Clusters 399 11.2.1 Chemical Reduction 399 11.2.1.1 Phosphorus Ligands 401 11.2.1.2 Sulfur Ligands 401 11.2.1.3 Amide Ligands 402 11.2.2 Physical Vapor Deposition 403 11.2.3 Electrical Reduction 404 11.2.4 Other Methods 404 11.3 Characterization of Gold Clusters 405 11.4 Catalysis by Gold Clusters 407 11.4.1 Selective Hydrogenation 407 11.4.2 Selective Oxidation 409 11.4.2.1 Oxygen Activation 409 11.4.2.2 Alkanes 410 11.4.2.3 Alkenes 411 11.4.2.4 Alcohols 414 11.4.3 CO Oxidation 415 11.4.4 Organic Synthesis 419 11.5 Conclusions and Perspectives 420 References 421 12 Asymmetric Phase–Transfer Catalysis in Organic Synthesis 425 Shen Li and Jun–An Ma 12.1 Introduction 425 12.2 Chiral Phase–Transfer Catalysts 426 12.2.1 Chiral Crown Ethers – Cation–Binding Phase–Transfer Catalysts 426 12.2.2 Chiral Cation Phase–Transfer Catalysts 428 12.2.2.1 Chiral Quaternary Ammonium Salts 428 12.2.2.2 Chiral Quaternary Phosphonium Salts 440 12.2.3 Chiral Anion Phase–Transfer Catalysts 441 12.3 Asymmetric Phase–Transfer Catalytic Reactions and Applications 443 12.3.1 Asymmetric Phase–Transfer Reactions of Glycine Imine Derivatives 443 12.3.1.1 Asymmetric Alkylations 443 12.3.1.2 Asymmetric Conjugate Additions 447 12.3.1.3 Asymmetric Aldol and Mannich Condensations 448 12.3.2 Asymmetric Phase–Transfer Reactions of 1,3–Dicarbony Derivatives 450 12.3.3 Asymmetric Phase–Transfer Reactions of Oxindoles 454 12.3.4 Asymmetric Phase–Transfer Reactions of Nitroalkanes 455 12.3.5 Asymmetric Phase–Transfer Cyclization Reactions 457 12.3.6 Asymmetric Phase–Transfer Fluorination and Trifluoromethylation Reactions 458 12.3.7 Asymmetric Phase–Transfer Cyanation Reactions 459 12.3.8 Other Asymmetric Phase–Transfer Reactions 460 12.4 Concluding Remarks 461 References 461 13 Catalysis in Supercritical Fluids 469 Zhaofu Zhang, Jun Ma, and Buxing Han 13.1 Introduction 469 13.2 Features of Supercritical Fluids and Related Catalytic Reactions 470 13.2.1 Properties of Supercritical Fluids 470 13.2.2 Features of Reactions in Supercritical Fluids 471 13.3 Examples of the Reactions in SCFs 472 13.3.1 Hydrogenation of Organic Substances 472 13.3.2 Hydrogenation of CO2 476 13.3.3 Hydroformylation Reactions 478 13.3.4 Oxidations 479 13.3.5 Alkylation 481 13.3.6 CO2 Cycloaddition to Epoxide 482 13.4 Summary and Conclusions 483 References 484 14 Hydroformylation of Olefins in Aqueous–Organic Biphasic Catalytic Systems 489 Hua Chen, Xueli Zheng, and Xianjun Li 14.1 Introduction 489 14.2 Water–Soluble Rhodium–Phosphine Complex Catalytic Systems 490 14.3 Mechanism 491 14.4 Hydroformylation of Lower Olefins 493 14.4.1 Ethylene 493 14.4.2 Propene 494 14.4.3 Butene 496 14.5 Hydroformylation of Higher Olefins 497 14.5.1 Supported Aqueous–Phase Catalysts 498 14.5.2 Cosolvent 499 14.5.3 Surfactants 500 14.5.4 Cyclodextrins 503 14.5.5 Thermoregulated Inverse Phase–Transfer Catalysts 505 14.6 Hydroformylation of Internal Olefins 506 14.7 Conclusion and Outlook 508 References 508 15 Recent Progress in Enzyme Catalysis in Reverse Micelles 511 Xirong Huang and Luyan Xue 15.1 Introduction 511 15.2 Enzyme Catalysis in Molecular Organic Solvent–Based Reverse Micelles 513 15.2.1 Effect of Interfacial Property of Reverse Micelles on Enzyme Catalysis 513 15.2.1.1 Effect of the Electrical Property of the Interface 513 15.2.1.2 Effect of the Size and Structure of Surfactant Head Group 516 15.2.2 Effect of Additives on Enzyme Catalysis in Reverse Micelles 521 15.2.2.1 Ionic Liquids as Additives 521 15.2.2.2 Nanomaterials as Additives 525 15.2.3 Relationship between the Conformation and the Activity of Enzymes in Reverse Micelles 528 15.2.4 Pseudophase Model and Enzyme–Catalyzed Reaction Kinetics in Reverse Micelles 530 15.3 Enzyme Catalysis in Ionic Liquid−Based Reverse Micelles 531 15.3.1 Microemulsification of Hydrophobic Ionic Liquids 531 15.3.2 Ionic Liquids as Surfactants 537 15.4 Application of Enzyme Catalysis in Reverse Micelles 537 15.4.1 Application in Biotransformation 538 15.4.2 Reverse Micelle–Based Gel and Its Application for Enzyme Immobilization 541 15.5 Concluding Remarks 543 References 544 16 The Molecular Kinetics of the Fischer–Tropsch Reaction 553 Rutger A. van Santen, Minhaj M. Ghouri, Albert J. Markvoort, and Emiel J. M. Hensen 16.1 Introduction 553 16.2 Basics of the Fischer–Tropsch Kinetics 556 16.2.1 Mechanistic Background of the Carbide–Based Mechanism 556 16.2.1.1 Initiation 557 16.2.1.2 Propagation 558 16.2.1.3 Termination 559 16.2.2 General Kinetics Considerations 559 16.2.2.1 Some Mathematical Expressions 559 16.3 Molecular Microkinetics Simulations 564 16.3.1 Analysis of Microkinetics Results 576 16.3.1.1 Monomer Formation Limited Kinetics Limit versus Chain Growth Model 576 16.3.1.2 Methane Formation versus Fischer–Tropsch Kinetics 583 16.4 The Lumped Kinetics Model 586 16.4.1 The Single Reaction Center Site Model 586 16.4.2 The Dual Reaction Center Site Model 592 16.5 Transient Kinetics 594 16.6 Conclusion and Summary 599 References 604 Index 607

Can Li received his PhD degree from the Dalian Institute of Chemical Physics (China) in 1988, was promoted to full professor in 1993, and was elected as a member of the Chinese Academy of Sciences in 2003. He was appointed director of the State Key Laboratory of Catalysis at the Dalian Institute of Chemical Physics in 1998 and elected to the President of the International Association of Catalysis Societies in 2008. He is a member of the editorial board of more than 15 academic journals and has published more than 400 peer–reviewed papers, authorized 40 patents and delivered more than 60 invited and plenary lectures at national and international conferences. Under his supervision, more than 60 graduate students have obtained their PhD degrees. Among the prestigious awards he received are the International Catalysis Award, the National Award for Outstanding Young Scientists in China, and the HoLeungHoLee Prize. His research interests are Physical Chemistry, Catalysis, Environmental Catalysis, Chiral Catalysis, Photocatalysis, Solar Energy Utilization (photocatalysis and photovoltaic), In–situ Characterization, Resonance and Time–resolved Spectroscopy. Yan Liu studied chemistry at Lanzhou University (China) and then moved to the State Key Laboratory of Organometallic Chemistry at the Shanghai Institute of Organic Chemistry to obtain his PhD degree under the supervision of Prof. Kuiling Ding in 2006. After three years of postdoctoral studies with Prof. Li Deng at Brandeis University (USA), he joined Prof. Can Li′s group at the State Key Laboratory of Catalysis at the Dalian Institute of Chemical Physics in 2010 as associate researcher.