Ionic liquids in synthesis: in 2 v. Vol.2 / ed. by Wasserscheid P., Welton T. - 2nd, completely revised and enlarged ed. - Weinheim: Wiley, 2008. - xxi, P.369-721. - ISBN 978-3-527-31239-9  Место хранения:   068 | Институт проблем химико - энергетических технологий CO РАН | Томск | Контактная информация о библиотеке

Оглавление / Contents

Preface to the Second Edition .................................. xv A Note from the Editors ....................................... xix Acknowledgements .............................................. xix List of Contributors .......................................... xxi Volume 2 5.3. Transition Metal Catalysis in Ionic Liquids .............. 369 Peter Wasserscheid and Peter Schulz 5.3.1. Concepts, Successful Strategies, and Limiting Factors ........................................... 372 5.3.1.1. Why Use Ionic Liquids as Solvents for Transition Metal Catalysis? .............. 372 5.3.1.2. The Role of the Ionic Liquid ............. 377 5.3.1.3. Methods for Analysis of Transition Metal Catalysts in Ionic Liquids ......... 383 5.3.2. Selected Examples of the Application of Ionic Liquids in Transition Metal Catalysis ............. 390 5.3.2.1. Hydrogenation ............................ 390 5.3.2.2. Oxidation Reactions ...................... 405 5.3.2.3. Hydroformylation ......................... 410 5.3.2.4. Heck Reaction and Other Pd-catalyzed C-C-coupling Reactions ................... 419 5.3.2.5. Dimerization and Oligomerization Reactions ................................ 430 5.3.2.6. Olefin Metathesis ........................ 441 5.3.2.7. Catalysis with Nanoparticulate Transition Metal Catalysts ............... 444 5.3.3. Concluding Remarks: "Low-hanging Fruits" and "High-hanging Fruits" - Which Transition Metal Catalyzed Reaction Should Be Carried Out in an Ionic Liquid? ..................................... 448 5.4. Ionic Liquids in Multiphasic Reactions ................... 464 Helene Olivier-Bourbigou and Frederic Favre 5.4.1. Multiphasic Reactions: General Features, Scope and Limitations ............................. 464 5.4.2. Multiphasic Catalysis: Limitations and Challenges ........................................ 465 5.4.3. Why Ionic Liquids in Mutiphasic Catalysis? ........ 466 5.4.4. Different Technical Solutions to Catalyst Separation through the Use of Ionic Liquids ....... 469 5.4.5. Immobilization of Catalysts in Ionic Liquids ...... 473 5.4.6. The Scale-up of Ionic Liquid Technology from Laboratory to Continuous Pilot Plant Operation .... 476 5.4.6.1. Dimerization of Alkenes Catalyzed by Ni complexes .......................... 477 5.4.6.2. Alkylation Reactions ..................... 483 5.4.6.3. Industrial Use of Ionic Liquids .......... 485 5.4.7. Concluding Remarks and Outlook .................... 486 5.5. Task-specific Ionic Liquids as New Phases for Supported Organic Synthesis .............................. 488 Michel Vaultier, Andreas Kirschning, and Vasundhara Singh 5.5.1. Introduction ...................................... 489 5.5.2. Synthesis of TSILs ................................ 490 5.5.2.1. Synthesis of TSILs Bearing a Hydroxy Group .................................... 491 5.5.2.2. Parallel Synthesis of Functionalized ILs from a Michael-type Reaction ......... 495 5.5.2.3. Synthesis of TSILs by Further Functional Group Transformations ......... 496 5.5.2.4. Loading of TSIL Supports ................. 500 5.5.3. TSILs as Supports for Organic Synthesis ........... 501 5.5.3.1. First Generation of TSILs as New Phases for Supported Organic Synthesis ... 503 5.5.3.2. Second Generation of TSILs: The BTSILs ... 510 5.5.3.3. Reactions of Functionalized TSOSs in Molecular Solvents ....................... 515 5.5.3.4. Lab on a Chip System Using a TSIL as a Soluble Support ..................... 523 5.5.4. Conclusion ........................................ 523 5.6. Supported Ionic Liquid Phase Catalysts ................... 527 Anders Riisager and Rasmus Fehrmann 5.6.1. Introduction ...................................... 527 5.6.2. Supported Ionic Liquid Phase Catalysts ............ 527 5.6.2.1. Supported Catalysts Containing Ionic Media .................................... 527 5.6.2.1.1. Process and engineering aspects of supported ionic liquid catalysts .............. 528 5.6.2.1.2. Characteristics of ionic liquids on solid supports ..... 529 5.6.2.2. Early Work on Supported Molten Salt and Ionic Liquid Catalyst Systems ............ 531 5.6.2.2.1. High-temperature supported molten salt catalysts ......... 531 5.6.2.2.2. Low-temperature supported catalysts ..................... 533 5.6.2.3. Ionic Liquid Catalysts Supported through Covalent Anchoring ............... 534 5.6.2.3.1. Supported Lewis acidic chlorometalate catalysts ...... 534 5.6.2.3.2. Neutral, supported ionic liquid catalysts .............. 537 5.6.2.4. Ionic Liquid Catalysts Supported through Physisorption or via Electrostatic Interaction ................ 540 5.6.2.4.1. Supported ionic liquid catalysts (SILC) .............. 540 5.6.2.4.2. Supported ionic liquid phase (SILP) catalysts incorporating metal complexes ............... 543 5.6.2.4.3. Supported ionic liquid catalyst systems containing metal nanoparticles ........... 552 5.6.2.4.4. Supported ionic liquid catalytic membrane systems containing enzymes ............ 554 5.6.3. Concluding Remarks ................................ 555 5.7. Multiphasic Catalysis Using Ionic Liquids in Combination with Compressed CO2 .......................... 558 Peter Wasserscheid and Sven Kuhlmann 5.7.1. Introduction ...................................... 558 5.7.2. Catalytic Reaction with Subsequent Product Extraction ........................................ 560 5.7.3. Catalytic Reaction with Simultaneous Product Extraction ........................................ 561 5.7.4. Catalytic Conversion of CO2 in an Ionic Liquid/scCO2 Biphasic Mixture ..................... 562 5.7.5. Continuous Reactions in an Ionic Liquid/Compressed CO2 System ...................... 562 5.7.6. Concluding Remarks and Outlook .................... 567 6. Inorganic Synthesis ........................................ 570 6.1. Directed Inorganic and Organometallic Synthesis .......... 569 Tom Welton 6.1.1. Coordination Compounds ............................ 569 6.1.2. Organometallic Compounds .......................... 570 6.1.3. Formation of Oxides ............................... 572 6.1.4. Other Reactions ................................... 574 6.1.5. Outlook ........................................... 574 6.2. Inorganic Materials by Electrochemical Methods ........... 575 Frank Endres and SherifZein El.Abedin 6.2.1. Electrodeposition of Metals and Semiconductors .... 576 6.2.1.1. General Considerations ................... 576 6.2.1.2. Electrochemical Equipment ................ 577 6.2.1.3. Electrodeposition of Less Noble Elements ................................. 578 6.2.1.4. Electrodeposition of Metals That Can Also Be Obtained From Water .............. 582 6.2.1.5. Electrodeposition of Semiconductors ...... 585 6.2.2. Nanoscale Processes at the Electrode/Ionic Liquid Interface .................................. 587 6.2.2.1. General Considerations ................... 587 6.2.2.2. The Scanning Tunneling Microscope ........ 587 6.2.2.3. Results .................................. 589 6.2.3. Summary ........................................... 604 6.3. Ionic Liquids in Material Synthesis: Functional Nanoparticles and Other Inorganic Nanostructures ......... 609 Markus Antonietti, Bernd Smarsly, and Yong Zhou 6.3.1. Introduction ...................................... 609 6.3.2. Ionic Liquids for the Synthesis of Chemical Nanostructures .................................... 609 7. Polymer Synthesis in Ionic Liquids ......................... 609 David M.Haddleton, Tom Welton, and Adrian J.Carmichael 7.1. Introduction ............................................. 619 7.2. Acid-catalyzed Cationic Polymerization and Oligomerization .......................................... 619 7.3. Free Radical Polymerization .............................. 624 7.4. Transition Metal-catalyzed Polymerization ................ 627 7.4.1. Ziegler-Natta Polymerization of Olefins ........... 627 7.4.2. Late Transition Metal-catalyzed Polymerization of Olefins ........................................ 628 7.4.3. Metathesis Polymerization ......................... 630 7.4.4. Living Radical Polymerization ..................... 631 7.5. Electrochemical Polymerization ........................... 633 7.5.1. Preparation of Conductive Polymers ................ 633 7.6. Polycondensation and Enzymatic Polymerization ............ 634 7.7. Carbene-catalyzed Reactions .............................. 635 7.8. Group Transfer Polymerization ............................ 636 7.9. Summary .................................................. 637 8. Biocatalytic Reactions in Ionic Liquids .................... 641 Sandra Klembt, Susanne Dreyer, Marrit Eckstein, and Udo Kragl 8.1. Introduction ............................................. 641 8.2. Biocatalytic Reactions and Their Special Needs ........... 641 8.3. Examples of Biocatalytic Reactions in Ionic Liquids ...... 644 8.3.1. Whole Cell Systems and Enzymes Other than Lipases in Ionic Liquids .......................... 644 8.3.2. Lipases in Ionic Liquids .......................... 651 8.4. Stability and Solubility of Enzymes in Ionic Liquids ..... 655 8.5. Special Techniques for Biocatalysis with Ionic Liquids ... 657 8.6. Conclusions and Outlook .................................. 658 9. Industrial Applications of Ionic Liquids ................... 663 Matthias Maase 9.1. Ionic Liquids in Industrial Processes: Re-invention of the Wheel or True Innovation? ......................... 663 9.2. Possible Fields of Application ........................... 664 9.3. Applications in Chemical Processes ....................... 666 9.3.1. Acid Scavenging: The BASILTM Process ............... 666 9.3.2. Extractive Distillation ........................... 669 9.3.3. Chlorination with "Nucleophilic HC1" .............. 670 9.3.4. Cleavage of Ethers ................................ 672 9.3.5. Dimerization of Olefins ........................... 673 9.3.6. Oligomerization of Olefins ........................ 673 9.3.7. Hydrosilylation ................................... 674 9.3.8. Fluorination ...................................... 675 9.4. Applications in Electrochemistry ......................... 675 9.4.1. Electroplating of Chromium ........................ 675 9.4.2. Electropolishing .................................. 676 9.5. Applications as Performance Chemicals and Engineering Fluids ................................................... 677 9.5.1. Ionic Liquids as Antistatic Additives for Cleaning Fluids ................................... 677 9.5.2. Ionic Liquids as Compatibilizers for Pigment Pastes ............................................ 678 9.5.3. Ionic Liquids for the Storage of Gases ............ 679 9.6. FAQ - Frequently Asked Questions Concerning the Commercial Use of Ionic Liquids ...................... 681 9.6.1. How Pure are Ionic Liquids? ....................... 681 9.6.2. Is the Color of Ionic Liquids a Problem? .......... 682 9.6.3. How Stable are Ionic Liquids? ..................... 682 9.6.4. Are Ionic Liquids Toxic? .......................... 683 9.6.5. Are Ionic Liquids Green? .......................... 684 9.6.6. How Can Ionic Liquids be Recycled? ................ 684 9.6.7. How Can Ionic Liquids be Disposed Of? ............. 685 9.6.8. Which is the Right Ionic Liquid? .................. 686 10. Outlook ................................................... 689 Peter Wasserscheid and Tom Welton Index ......................................................... 705