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

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

Can Li (Editor), Yan Liu (Editor)

ISBN: 978-3-527-67590-6

Apr 2014

656 pages

Description

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.
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

2.2.2 Characterization of IL-Supported or Mediated MNPs 28

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

2.2.8 Brief Summary 49

2.3 Reactions Catalyzed by Solid-Supported IL: Heterogeneous Catalysis with Homogeneous Performance 50

2.3.1 Introduction 50

2.3.2 Design, Preparation, and Properties of Silica Gel-Confined IL Catalysts 55

2.3.3 Catalytic Reaction with Supported IL Catalysts 57

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

3.2.3 Periodic Mesoporous Organosilicas (PMOs) 96

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

3.3.2 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

5.2.3 Zn Complex-Catalyzed Enantioselective Reactions 159

5.2.4 Ru Complex-Catalyzed Enantioselective Reactions 168

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

5.4 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

6.2.3 C–C Bond Formation 220

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

10.3 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

10.4 Catalytic Reactions in Nanoreactors 369

10.4.1 Pore Confinement Effect 369

10.4.2 Enhanced Cooperative Activation Effect in Nanoreactors 377

10.4.3 Isolation Effect in Nanoreactors 382

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

11.2.2 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

11.4.3 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

12.2.3 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

12.3.2 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

15.2.2 Effect of Additives on Enzyme Catalysis in Reverse Micelles 521

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

16.2.2 General Kinetics Considerations 559

16.3 Molecular Microkinetics Simulations 564

16.3.1 Analysis of Microkinetics Results 576

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