Advances in Organometallic Chemistry (eBook)

Pedro J. Perez (Herausgeber)

eBook Download: PDF | EPUB

2014 | 1. Auflage
322 Seiten
Elsevier Science (Verlag)
978-0-12-801084-6 (ISBN)

Infos

This book contains authoritative reviews regarding the field of Organometallic Chemistry, written by highly qualified experts within the area, and reviewed by other experts before publication. Because of this high standard, AOC is one of the most cited journals in both Organic and Inorganic Chemistry fields. - High quality of the articles - Expertise of authors - Careful editing that provides an easy-to-read material

Inhalt

Front Cover 1
Advances in Organometallic Chemistry 4
Copyright 5
Contents 6
Contributors 8
Chapter One: Palladium-Mediated Organofluorine Chemistry 10
1. Introduction 10
2. CC Coupling Reactions of Fluorinated Reagents 12
2.1. Overview of catalytic CC coupling reactions of fluorinated derivatives 12
2.1.1. CC coupling of fluorinated alkyl derivatives 13
2.1.1.1. Radical reactions 14
2.1.1.2. Perfluoroalkyl groups in the Stille reaction 16
2.1.1.3. Introduction of fluorinated groups using the Negishi reaction 17
2.1.1.4. Introduction of fluorinated groups using the Suzuki reaction 18
2.1.1.5. Use of fluoroalkyl silanes as fluoroalkylating reagents 21
2.1.1.6. Other fluoroalkylating reagents: Fluoroalkyl copper 22
2.1.1.7. Allylic alkylation reactions 25
2.1.1.8. Catalysis through palladium mediated CH activation 27
2.1.1.9. Perfluoroalkylation of unsaturated molecules 29
2.1.2. CC coupling of fluorinated aryl derivatives 31
2.1.2.1. Heck reactions 31
2.1.2.2. Suzuki-Miyaura reactions 31
2.1.2.3. Stille reactions 33
2.1.2.4. Sonogashira reactions 33
2.1.3. CC coupling of fluorinated arenes 34
2.1.4. CC coupling of fluorinated alkenyls 37
2.2. The PdRF bond 40
2.2.1. PdAlkylF bonds 40
2.2.2. PdArF bonds 41
2.3. Elementary steps in organofluorine CC coupling palladium-catalyzed processes 44
2.3.1. Oxidative addition and related processes 45
2.3.1.1. Oxidative addition to Pd(0) compounds 45
2.3.1.2. Oxidation of Pd(II) compounds leading to organofluorine Pd(IV) derivatives 47
2.3.2. Transmetalation 49
2.3.2.1. The transmetalation step in the Stille reaction 50
2.3.2.2. Transmetalation equilibria between organogold and organopalladium complexes 54
2.3.2.3. The transmetalation step in the Negishi reaction 56
2.3.3. Reductive elimination 58
2.3.3.1. Reductive elimination from Pd(II) complexes 58
2.3.3.2. Reductive elimination from Pd(IV) complexes 62
2.3.4. 2,1-Insertion 63
2.3.5. 1,1-Insertion (migratory insertion) 68
3. CF Activation and Fluorination 70
3.1. Overview of catalytic CC and CX coupling reactions where a CF bond is cleaved 71
3.1.1. CC coupling reactions of fluorinated aryls 71
3.1.2. CC Coupling reactions of fluorinated alkenes 75
3.1.3. Allylic substitutions of a fluorine atom 75
3.1.4. Hydrodefluorination reactions 75
3.2. Overview of catalytic CF forming reactions 78
3.2.1. Pd-catalyzed fluorination with electrophilic fluorine sources 79
3.2.2. Pd-catalyzed fluorination with nucleophilic fluorine sources 83
3.3. The PdF bond 86
3.4. Oxidative addition of RF 90
3.5. ß-F and a-F elimination 94
3.6. Other activation routes for CF cleavage 95
3.7. Reductive elimination of RF 96
4. Conclusion 101
Acknowledgment 101
References 101
Chapter Two: Normal and Abnormal N-Heterocyclic Carbene Ligands: Similarities and Differences of Mesoionic C-Donor Complexes 120
1. Introduction and General Considerations 120
2. Ligand Nomenclature: Abnormal or Mesoionic Carbene Complexes? 124
3. Electronic Considerations 126
4. Reactivity of Complexes with Sterically Comparable Ligands 130
4.1. Imidazolylidene complexes 131
4.1.1. Structure and electronics of normal versus abnormal mesoionic imidazolylidene complexes 131
4.1.2. Comparative evaluation of imidazolylidene complexes in hydrogenation catalysis and related transformations 138
4.1.3. Comparative evaluation of imidazolylidene complexes in cross-coupling catalysis 144
4.2. N,X-Heterocyclic carbene complexes 146
4.3. Triazolylidene complexes 148
4.4. Pyridylidene complexes 150
4.4.1. Monodentate pyridylidene complexes 150
4.4.2. Polydentate pyridylidene complexes 155
4.4.3. Catalytic applications of pyridylidene complexes 156
5. Conclusions and Outlook 156
Acknowledgments 158
References 158
Chapter Three: Synthesis and Applications in Catalysis of Metal Complexes with Chelating Phosphinosulfonate Ligands 168
1. Introduction 169
2. Synthetic Routes to Achiral and Racemic Phosphine Sulfonic Acid Prochelates 170
2.1. Preparation of phosphinoalkylsulfonates 170
2.2. Preparation of symmetrical phosphinoarylsulfonic acids 172
2.3. Preparation of racemic P-stereogenic phosphinoarylsulfonic acids 175
2.4. Preparation of miscellaneous sulfonate prochelates 178
2.4.1. Polysulfonated o-phosphinoarylsulfonates 178
2.4.2. Phosphinoarylsulfonates 180
2.4.3. Racemic ferrocenylphosphinosulfonate 180
2.4.4. Diazaphospholidinobenzenesulfonates 180
2.4.5. Imidazolium sulfonate zwitterions 182
3. Preparation of Scalemic Sulfonate Prochelates 184
3.1. Phosphinoferrocenesulfonates 184
3.2. P-chiral phosphinobenzenesulfonates 185
3.3. Enantiopure phosphinoethanesulfonates 185
3.4. Atropoisomeric phosphinobenzenesulfonates 186
3.5. Enantiopure imidazoliniumbenzenesulfonates 187
4. Applications of Sulfonate Prochelates in Coordination Chemistry 187
4.1. Transition metal complexes bearing phosphinosulfonate ligand 187
4.1.1. Palladium complexes 189
4.1.1.1. Neutral [(PO)2Pd] complexes 189
4.1.1.2. Anionic [Pd(PO)R]- complexes 189
4.1.1.3. Neutral allylic [Pd(PO)] complexes 190
4.1.1.4. Formation of palladium(alkyl)(PO) complexes 190
4.1.2. Nickel complexes 194
4.1.3. Platinum complexes 196
4.1.4. Rhodium and iridium complexes 197
4.1.5. Ruthenium complexes 198
4.2. Transition metal complexes bearing NHC-sulfonate ligand 199
5. Applications in Molecular Catalysis 201
5.1. Ruthenium-catalyzed activation of allylic alcohols 201
5.2. Hydrogenation/hydrogen (auto)transfers 203
5.2.1. Iridium-catalyzed hydrogenation of alkenes 203
5.2.2. Ruthenium-catalyzed hydrogenation of ketones 204
5.2.3. C(3)-alkylation of saturated amines through hydrogen autotransfer 205
5.3. Rhodium-catalyzed hydroformylation 208
5.4. Copper-catalyzed conjugate addition 208
5.5. Copper-catalyzed asymmetric allylic alkylation 209
5.6. Miscellaneous reactions catalyzed by phoshinesulfonate metal complexes 211
6. Application of Metal-Phosphinosulfonate Chelate Complexes in Polymerization 213
6.1. Oligo- and polymerization of ethylene 213
6.2. Copolymerization of ethylene with polar monomers 215
6.3. Copolymerization of ethylene with carbon monoxide 216
6.4. Copolymerization of polar monomers with carbon monoxide 217
7. Recent Contributions 218
8. Conclusions and Outlook 218
Acknowledgments 219
References 219
Chapter Four: The Mannich Route to Amino-Functionalized [3]Ferrocenophanes 228
1. Introduction 228
2. Prolog: Synthesis of Ansa-Zirconocenes by the Mannich Reaction 230
3. [3]Ferrocenophane Synthesis by the Mannich Route 232
4. [3]Ferrocenophane Derived N/P and P/P Chelate Ligands 244
5. [3]Ferrocenophanes in Bio-Organometallic Chemistry 250
6. Frustrated Lewis Pair Chemistry at the [3]Ferrocenophane Framework 253
7. Some Conclusions 257
Acknowledgments 257
References 258
Chapter Five: Organometallic Intermediates of Gold Catalysis 270
1. Introduction 270
2. Organogold Intermediates 271
2.1. p-Complexes 271
2.1.1. Alkene gold complexes 271
2.1.2. Arene gold complexes 273
2.1.3. Allene gold complexes 275
2.1.4. Alkyne gold complexes 275
2.2. Vinylic organogold complexes 279
2.3. Alkylgold complexes 286
2.4. Gold hydrides 288
2.5. Gem-diaurated complexes and gold acetylides 289
2.6. Gold carbenoids 294
2.7. Gold(III) intermediates 297
3. Conclusions 298
References 299
Index 308

Textauszug

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Produkt-Details

• Erscheint lt. Verlag: 25.9.2014
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Technik
• ISBN-10: 0-12-801084-3 / 0128010843
• ISBN-13: 978-0-12-801084-6 / 9780128010846