Home Shop Service Stellenangebote Newsletter Das Unternehmen Shopping cart English
Bücher | Chemie | Organische Chemie | Aqueous-Phase Organometallic Catalysis | Inhaltsverzeichnis
Unsere Produkte
Bücher
 
Soeben erschienen
Titelsuche
Featured Sites
Zeitschriften
Wählen Sie Ihr Fachgebiet
 
  Contents  
 
1 Introduction 1
1 Introduction
(B. Cornils, W.A. Herrmann) 		3
2 Basic Aqueous Chemistry 25
2.1 Organic Chemistry in Water
(A. Lubineau, J. Augé, M.-C. Scherrmann) 		27
2.1.1 Introduction 27
2.1.2 Origin of the Reactivity in Water 28
2.1.3 Pericyclic Reactions 30
2.1.3.1 Diels - Alder Reactions 30
2.1.3.2 Hetero Diels - Alder Reactions 32
2.1.3.3 Other Cycloadditions 33
2.1.3.4 Claisen Rearrangements 33
2.1.4 Carbonyl Additions 34
2.1.4.1 Aldol-type Reactions 34
2.1.4.2 Michael-type Reactions 36
2.1.4.3 Allylation Reactions 36
2.1.5 Oxido-reductions 38
2.1.5.1 Oxidations 38
2.1.5.2 Reductions 38
2.1.6 Radical Reactions 39
2.1.7 Outlook 40
2.2 Organometallic Chemistry in Water
(W.A. Herrmann, F.E. Kühn) 		44
2.2.1 Introduction 44
2.2.2 Water as a Solvent and Ligand 44
2.2.3 Organometallic Reactions of Water 46
2.2.4 Catalytic Reactions with Water 50
2.2.4.1 Water-gas Shift Reaction 50
2.2.4.2 Wacker - Hoechst Acetaldehyde Process 50
2.2.4.3 Olefin Hydration 51
2.2.4.4 Hydrodimerization 51
2.2.5 Water-soluble Metal Complexes 52
2.2.6 Perspectives 52
2.3 Characterization of Organometallic Compounds in Water
(G. Laurenczy) 		57
2.3.1 Introduction 57
2.3.2 General Survey 57
2.3.3 Effect of High Hydrostatic Pressure on Aqueous Organometallic Systems 59
2.3.4 Aqueous Organometallics with Pressurized Gases 62
2.3.5 Concluding Remarks 65
3 Catalysts for an Aqueous Catalysis 69
3.1 Variation of Central Atoms 71
3.1.1 Transition Metals
(D.J. Darensbourg, C.G. Ortiz) 		71
3.1.1.1 Introduction 71
3.1.1.2 Water-soluble Catalysts by Virtue of Water-soluble Ligands 72
3.1.1.3 Water-soluble Catalysts through Water Coordination 82
3.1.2 Lanthanides in Aqueous-phase Catalysis
(S. Kobayashi) 		88
3.1.2.1 Introduction 88
3.1.2.2 Aldol Reactions 89
3.1.2.3 Mannich-type Reactions 90
3.1.2.4 Diels - Alder Reactions 91
3.1.2.5 Micellar Systems 92
3.1.2.6 Asymmetric Catalysis in Aqueous Media 95
3.1.2.7 Conclusions 97
3.2 Variation of Ligands 100
3.2.1 Monophosphines
(O. Stelzer†, S. Rossenbach, D. Hoff) 		100
3.2.1.1 General Features, Scope, and Limitations 100
3.2.1.2 Anionic Phosphines 101
3.2.1.3 Cationic Phosphines 112
3.2.1.4 Nonionic Water-soluble Phosphines 115
3.2.2 Diphosphines and Other Phosphines
(M. Schreuder Goedheijt, P.C.J. Kamer, J.N.H. Reek, P.W.N.M. van Leeuwen) 		121
3.2.2.1 General 121
3.2.2.2 Diphosphines - Introduction of Sulfonate Groups by Direct Sulfonation 121
3.2.2.3 Introduction of Sulfonate Groups During Synthesis 123
3.2.2.4 Diphosphines with Quaternized Aminoalkyl or Aminoaryl Groups 125
3.2.2.5 Diphosphines with Hydroxyalkyl or Polyether Substituents 125
3.2.2.6 Carboxylated Diphosphines 128
3.2.2.7 Amphiphilic Diphosphines 129
3.2.2.8 Other Phosphines 130
3.2.3 Ligands or Complexes Containing Ancillary Functionalities
(P. Kalck, M. Urrutigoity) 		137
3.2.3.1 Complexes Containing at Least Two Classical Functionalities 137
3.2.3.2 Cationic Complexes 140
3.2.3.3 Immobilization on Silica Supports 143
3.2.3.4 Macromolecular Ligands or Supports 145
3.2.3.5 Ligands not Containing Phosphorus 151
3.2.3.6 Additional Perspectives 154
3.2.4 Tenside Ligands
(G. Papadogianakis) 		158
3.2.4.1 Introduction 158
3.2.4.2 Tenside Phosphines and Amines 159
3.2.4.3 Hydroformylation Reactions Catalyzed by Transition Metal Surfactant - Phosphine Complexes 161
3.2.4.4 Hydrogenation Reactions Catalyzed by Transition Metal Surfactant - Phosphine Complexes 168
3.2.4.5 Carbonylation Reactions Catalyzed by Transition Metal Surfactant - Phosphine Complexes 171
3.2.4.6 Concluding Remarks and Future Prospects 171
3.2.5 Chiral Ligands
(W.A. Herrmann, R.W. Eckl, F.E. Kühn) 		174
3.2.5.1 Introduction 174
3.2.5.2 Sulfonated Chiral Phosphines 174
3.2.5.3 Other Water-soluble Chiral Ligands 181
3.2.5.4 Conclusions 185
3.2.6 Other Concepts
(A. Börner) 		187
3.2.6.1 Hydroxyphosphines as Ligands 187
3.2.6.2 Amines and Polyoxometallates as Ligands
(W.A. Herrmann, C.-P. Reisinger) 		194
4 Catalysis in Water as a Special Unit Operation 199
4.1 Fundamentals of Biphasic Reactions in Water
(Y. Önal, M. Baerns, P. Claus) 		201
4.1.1 Introduction 201
4.1.2 Gas/Liquid-phase Reactions 203
4.1.3 Gas/Liquid/Liquid-phase Reactions 207
4.1.4 Place of Reaction in Aqueous Biphasic Systems 212
4.2 Technical Concepts
(A. Behr) 		219
4.2.1 Reaction Systems 219
4.2.2 Technical Realization: Variations 221
4.2.2.1 Reaction with Product Separation 223
4.2.2.2 Reaction and Product Extraction 224
4.2.2.3 Reaction and Product Treatment 227
4.2.2.4 Reaction and Catalyst Separation 227
4.2.2.5 Reaction and Catalyst Extraction 229
4.2.2.6 Reaction and Catalyst Treatment 231
4.2.3 Reaction Engineering Aspects 233
4.2.4 New Developments 234
4.2.4.1 Telomerization 234
4.2.4.2 Oligomerization 235
4.2.4.3 Hydrogenation 236
4.2.4.4 Hydroformylation 236
4.2.4.5 Other Reactions 237
4.3 Side Effects, Solvents, and Co-solvents
(B.E. Hanson) 		243
4.3.1 Introduction 243
4.3.2 Hydroformylation 244
4.3.3 Hydrogenations and Other Catalytic Reactions 248
4.4 Membrane Techniques
(H. Bahrmann, B. Cornils) 		252
4.5 Micellar Systems
(G. Oehme) 		256
4.5.1 Introduction 256
4.5.2 Hydrolytic Reactions in Micelles 259
4.5.3 Oxidation Reactions in Micelles 260
4.5.4 Complex-catalyzed Hydrogenation in Micellar Media 261
4.5.5 Carbon - Carbon Coupling Systems 264
4.5.6 Some Examples of Reactions in Reverse Micelles and Microemulsions 266
4.5.7 Perspectives 267
4.6 On the Borderline of Aqueous-phase Catalysis 272
4.6.1 Phase-transfer Catalysis
(E.V. Dehmlow) 		272
4.6.1.1 General Overview, Fundamentals, and Definitions 272
4.6.1.2 Aqueous Organic-phase Heck and Other Cross Couplings under Phase-transfer Catalysis Conditions 275
4.6.1.3 Hydrogenations Mediated by Phase-transfer Catalysts 278
4.6.1.4 Biphasic Transfer Hydrogenations 280
4.6.1.5 Aqueous/Organic-phase Oxidations Mediated by Metal and PT Catalysts 280
4.6.1.6 Aqueous/Organic-phase Carbonylations 282
4.6.2 Counter-phase Transfer Catalysis
(T. Okano) 		288
4.6.2.1 Introduction 288
4.6.2.2 Mechanism of the Counter-phase Transfer Catalytic Reaction 290
4.6.2.3 Counter-phase Transfer Catalytic Reactions 293
4.6.2.4 Concluding Remarks 297
4.6.3 Thermoregulated Phase-transfer and Thermoregulated Phase-separable Catalysis
(Z. Jin, Y. Wang, X. Zheng) 		301
4.6.3.1 Introduction 301
4.6.3.2 Thermoregulated Phase-transfer Catalysis with Nonionic Water-soluble Phosphines 302
4.6.3.3 Hydroformylation of Higher Alkenes Based on TRPTC 305
4.6.3.4 Thermoregulated Phase-separable Catalysis 307
4.6.3.5 Conclusions 311
4.7 Transitions to Heterogeneous Techniques (SAPC and Variations)
(M.E. Davis) 		313
4.7.1 Introduction 313
4.7.2 The SAPC Concept of Immobilization 314
4.7.3 Example of Rational Catalyst Design Strategy 318
4.7.4 Suggested Reactions for Implementation of Design Concepts 321
4.7.5 Outlook 322
5 Aqueous Catalysts for Environment and Safety 325
5.1 Water-soluble Organometallics in the Environment
(W.A. Herrmann, F.E. Kühn) 		327
5.1.1 Introduction 327
5.1.2 Biological Methylation 327
5.1.3 Cobalamines - Organometallics in Nature 328
5.1.4 Organoarsenic and Organotin Compounds 330
5.1.5 Organomercury Compounds 331
5.1.6 Other Metal-alkyl Complexes in the Environment 332
5.1.7 Perspectives 334
5.2 Environmental and Safety Aspects
(B. Cornils, E. Wiebus) 		337
5.2.1 Introduction 337
5.2.2 The Ruhrchemie/Rhône-Poulenc (RCH/RP) Process 338
5.2.3 Crucial Environmental Improvements 342
5.2.4 Conclusions 345
6 Typical Reactions 349
6.1 Hydroformylation 351
6.1.1 Development of the Commercial Biphasic Oxo Synthesis
(B. Cornils, E.G. Kuntz) 		351
6.1.1.1 History of Biphasic Catalysis 351
6.1.1.2 Basic Work and Investigations by Rhône-Poulenc 353
6.1.1.3 Investigations by Ruhrchemie AG 355
6.1.1.4 The RCH/RP Process as the Final Point of Development 358
6.1.2 Kinetics
(R.V. Chaudhari, B.M. Bhanage) 		364
6.1.2.1 Introduction 364
6.1.2.2 Kinetics Using Water-soluble Catalysts 365
6.1.2.3 Concluding Remarks 375
6.1.3 Reaction of Alkenes 377
6.1.3.1 Lower Alkenes
(C.D. Frohning, C.W. Kohlpaintner) 		377
6.1.3.2 Higher Alkenes
(H. Bahrmann, S. Bogdanovic, P.W.N.M. van Leeuwen) 		391
6.1.3.3 Functionalized Alkenes
(E. Monflier, A. Mortreux) 		410
6.1.4 Re-immobilization Techniques
(H. Bahrmann) 		417
6.1.4.1 Introduction 417
6.1.4.2 Water-insoluble, Re-immobilized Liphophilic Ligands and Their Separation by Membrane Technique 418
6.1.4.3 Separation and Use of Water-insoluble Ammonium Ligands in Hydroformylation 419
6.1.4.4 Separation of Phosphine Oxides and Other Degradation Products 426
6.1.4.5 Further Developments 426
6.2 Hydrogenation
(F. Joó, A. Kathó) 		429
6.2.1 Introduction 429
6.2.2 Mechanisms and Catalysts of Hydrogenations in Aqueous Solution 430
6.2.2.1 Basic Mechanisms of Dihydrogen Activation 430
6.2.2.2 Water-soluble Hydrogenation Catalysts with Tertiary Phosphine Ligands 431
6.2.2.3 Complexes of Ligands with Donor Atoms Other Than Phosphorus(III) 440
6.2.3 Typical Reactions 441
6.2.3.1 Hydrogenation of Compounds with C = C and C = C Bonds 441
6.2.3.2 Hydrogenation of Compounds with C = O and C = N Bonds 451
6.2.3.3 Hydrogenolysis of C - O, C - N, C - S, and C - Halogen Bonds 456
6.2.3.4 Miscellaneous Hydrogenations 458
6.3 Hydrogenation and Hydrogenolysis of Thiophenic Molecules
(C. Bianchini, A. Meli) 		464
6.3.1 Introduction 464
6.3.2 Hydrogenation Reactions 465
6.3.3 Hydrogenolysis Reactions 467
6.3.4 Future Developments 471
6.4 Oxidations 473
6.4.1 Partial Oxidations
(R.A. Sheldon, G. Papadogianakis) 		473
6.4.1.1 Introduction 473
6.4.1.2 Water-soluble Ligands 474
6.4.1.3 Concluding Remarks 479
6.4.2 Wacker-type Oxidations
(E. Monflier, A. Mortreux) 		481
6.4.2.1 Possibilities of Wacker-type Oxidations 481
6.4.2.2 Conclusions 486
6.4.3 Methyltrioxorhenium(VII) as an Oxidation Catalyst
(F.E. Kühn, W.A. Herrmann) 		488
6.4.3.1 Introduction 488
6.4.3.2 Synthesis of Methyltrioxorhenium(VII) 488
6.4.3.3 Behavior of Methyltrioxorhenium in Water 489
6.4.3.4 Catalyst Formation and Applications in Alkene Epoxidation 490
6.4.3.5 Other Oxidation Reactions 494
6.4.3.6 Perspectives 498
6.5 Carbonylation Reactions
(M. Beller, J.G.E. Krauter) 		501
6.5.1 Introduction 501
6.5.2 Reductive Carbonylations 501
6.5.3 Carboxylation of C-X Derivatives 503
6.5.4 Hydrocarboxylation of Alkenes 508
6.5.5 Conclusions 508
6.6 C - C Coupling Reactions (Heck, Stille, Suzuki, etc.)
(W.A. Herrmann, C.-P. Reisinger, P. Härter) 		511
6.6.1 Introduction 511
6.6.2 Catalysts and Reaction Conditions 512
6.6.3 Olefination 513
6.6.4 Alkyne Coupling 516
6.6.5 Cross-coupling Reactions 518
6.6.5.1 Suzuki Coupling 518
6.6.5.2 Stille Coupling 519
6.6.5.3 Miscellaneous 521
6.6.6 Conclusions 521
6.7 Hydrocyanation
(H.E. Bryndza, J.A. Harrelson, Jr.) 		524
6.7.1 Introduction 524
6.7.2 HCN as a Synthon 524
6.7.2.1 Michael Additions of HCN to Activated Alkenes 524
6.7.2.2 Synthesis of Cyanohydrins from Ketones and Aldehydes 525
6.7.2.3 Strecker Synthesis of Aminonitriles 526
6.7.2.4 HCN Addition to Unactivated C = C Double Bonds 526
6.7.2.5 Cyanide Coupling Reactions 528
6.7.3 Summary 529
6.8 Allylic Substitution
(D. Sinou) 		532
6.8.1 Introduction 532
6.8.2 Scope of the Reaction 532
6.8.3 Applications 535
6.8.4 Conclusions 538
6.9 Hydrodimerization
(N. Yoshimura) 		540
6.9.1 Introduction 540
6.9.2 Development of Technologies 542
6.9.3 Process of the Manufacture of 1-Octanol and Other Derivatives 545
6.9.4 Applications 547
6.10 Alkene Metathesis
(R.H. Grubbs, D.M. Lynn) 		550
6.10.1 Introduction 550
6.10.2 "Classical" Group VIII Catalysts 551
6.10.3 Polymers Prepared via Aqueous ROMP 554
6.10.4 Alkylidenes as Catalysts 556
6.10.4.1 Well-defined Ruthenium Alkylidenes 556
6.10.4.2 Water-soluble Alkylidenes 557
6.10.5 Summary 564
6.11 Asymmetric Synthesis
(D. Sinou) 		567
6.12 Catalytic Polymerization
(S. Mecking) 		576
6.12.1 Introduction 576
6.12.2 Copolymerization of Carbon Monoxide with Alkenes 577
6.12.3 Polymerization of Ethylene and 1-Alkenes 578
6.12.4 Polymerization of Conjugated Dienes 581
6.12.5 Vinyl-type Polymerization of Cyclic Alkenes 582
6.12.6 Ring Opening Metathesis Polymerization 583
6.12.7 Polymerization of Alkynes 587
6.12.8 Polymerization by Suzuki Coupling 587
6.12.9 Summary and Outlook 589
6.13 Oleochemistry
(A. Behr) 		593
6.13.1 Introduction 593
6.13.2 Hydrogenation 593
6.13.3 Hydroformylation 597
6.13.4 Hydrocarboxylation 599
6.13.5 Oxidation 600
6.13.6 Oligomerization 602
6.13.7 Hydrosilylation 602
6.13.8 Isomerization 603
6.14 Halogen Chemistry
(M. Bressan, A. Morvillo) 		606
6.14.1 Introduction 606
6.14.2 Reductive and Oxidative Dehalogenation 606
6.14.3 Coupling and Carbonylation Reactions 609
6.15 Biological Conversions
(P.J. Quinn) 		613
6.15.1 Introduction 613
6.15.2 Biological Substrates 613
6.15.3 Hydrogenation of Unsaturated Lipids in Aqueous Dispersions 614
6.15.3.1 Water-insoluble Homogeneous Catalysts 616
6.15.3.2 Water-soluble Homogeneous Catalysts 617
6.15.3.3 Sources of Hydrogen 619
6.15.4 Hydrogenation of Biological Membranes 620
6.15.4.1 Topology of Unsaturated Lipids in Membranes 620
6.15.4.2 Function of Unsaturated Lipids in Membranes 621
6.15.4.3 Acclimation of Membranes to Low Temperature 622
6.15.4.4 Membrane Unsaturation and Stability at High Temperatures 622
6.15.4.5 Biochemical Homeostasis of Unsaturated Lipids 623
6.15.4.6 Hydrogenation of Living Cells 624
6.15.5 Conclusions 625
6.16 Other Recent Examples
(W.A. Herrmann, A.M. Santos, F.E. Kühn) 		627
6.16.1 Introduction 627
6.16.2 Isomerizations 627
6.16.3 Aldolizations 628
6.16.4 Hydroaminomethylation 630
6.15.5 Aminations 631
6.16.6 Hydrosilylations 631
6.16.7 Thiolysis 632
6.16.8 Synthesis of Various Heterocycles 633
7 Other Biphasic Concepts 637
7.1 Nonaqueous Organic/Organic Separation (SHOP Process)
(D. Vogt) 		639
7.1.1 Introduction 639
7.1.2 Process Description 640
7.2 Catalysis in Fluorous Phases
(J.T. Horváth) 		646
7.2.1 Introduction 646
7.2.2 The Fluorous Concept 646
7.2.3 Process and Applications 650
7.3 Nonaqueous Ionic Liquids (ILs, NAILs)
(H. Olivier-Bourbigou) 		655
7.3.1 Introduction 655
7.3.2 NAILs as a New Class of Solvents 655
7.3.3 Applications in Organic Synthesis and Catalysis 657
7.3.3.1 Salts Containing Strongly Coordinating Anions to Stabilize Anionic Complexes 657
7.3.3.2 Salts Containing Weakly Coordinating Anions for Cationic and Molecular Complexes 658
7.3.3.3 Salts Containing Chloroaluminate Anions as Solvents and Acidic Catalysts 660
7.3.3.4 Supported Ionic Liquid Catalysis 661
7.3.3.5 Solvents for Organic Reactions 661
7.3.4 Concluding Remarks 662
7.4 Immobilization of Organometallic Catalysts Using Supercritical Fluids
(W. Leitner, A.M. Scurto) 		665
7.4.1 Introduction 665
7.4.2 Practical Approaches to Multiphase Catalysis Involving Supercritical Fluids 668
7.4.2.1 Supercritical Fluids and Supported Catalysts 668
7.4.2.2 Liquid/Supercritical Biphasic Systems 672
7.4.2.3 Catalysis and Extraction Using sc Solutions (CESS) 678
7.4.3 Conclusions and Outlook 682
7.5 The Amphiphilic Approach
(P.C.J. Kamer, J.N.H. Reek, P.W.N.M. van Leeuwen) 		686
7.5.1 Separation Methods 686
7.5.1.1 Two-phase Catalysis 686
7.5.1.2 The Extraction Concept 688
7.5.2 Use of Amphiphilic Phosphines 690
7.5.2.1 Catalysis Using Amphiphilic Ligands 690
7.5.2.2 Distribution Characteristics of the Free Ligands 693
7.5.2.3 Rhodium Recycling 696
7.5.3 Conclusions 697
7.6 Catalysis with Water-soluble Polymer-bound Ligands in Aqueous Solution
(S. Mecking, E. Schwab) 		699
7.6.1 Introduction 699
7.6.2 Catalysis with Water-soluble Polymer-bound Ligands in Aqueous Solution 700
7.6.3 Conclusions 704
8 Aqueous-phase Catalysis: The Way Ahead 707
8.1 State of the Art
(B. Cornils, W.A. Herrmann) 		709
8.2 Improvements to Come 712
8.2.1 Reaction Engineering 713
8.2.2 Other Technologies 714
8.2.3 Other Feedstocks and Reactions 715
8.3 Focal Future Developments 717
Subject Index 727

 
Bestellen
Online-Ausgabe
Inhaltsverzeichnis
Kurzbeschreibung
Langtext
Besprechungen
Sitz der Autoren

Weitere Bücher

Arrow-Pushing in Inorganic Chemistry
A Logical Approach to the Chemistry of the Main Group Elements

NMR in Organometallic Chemistry

Fundamentals of Organometallic Catalysis


[mehr >>]

Weitere Zeitschriften

Angewandte Chemie

Angewandte Chemie International Edition

Chemie Ingenieur Technik


[mehr>>]

Angebot

Krämer, Wolfgang / Schirmer, Ulrich / Jeschke, Peter / Witschel, Matthias (eds.)

Modern Crop Protection Compounds
449,- Euro
gültig bis
30. Juni 2012

[mehr Angebote >>]


 

        

Seite empfehlen          RSS-Feeds         Druckversion         Sitemap

©2012 Wiley-VCH Verlag GmbH & Co. KGaA - Betreiber
http://www.wiley-vch.de - mailto: info@wiley-vch.de
Datenschutz