Die vorliegende Dissertation beschäftigt sich mit der Synthese, der Charakterisierung und der Anwendung neuartiger Phosphane in homogenkatalytischen Reaktionen. Dabei wurden die Ferrocenyl- und Ferrocenylethinylphosphan-Palladium und Ferrocenylethinylphosphan-Ruthenium Komplexe in der Palladium-vermittelten Mizoroki-Heck- und Suzuki-Miyaura-Reaktion sowie der Ruthenium-katalysierten Synthese von β-Oxopropylestern verwendet. Der Schwerpunkt lag dabei auf der Untersuchung des Einflusses der elektronischen und räumlichen Eigenschaften der Phosphanliganden auf die Aktivität und Produktivität der entsprechenden Katalysatoren in den homogenkatalytischen Reaktionen.
Weiterhin beschäftigt sich die vorliegende Arbeit mit der Synthese und Charakterisierung von funktionalisierten (Phosphino)Imidazol und (Phosphino)Imidazolium Salzen und deren Anwendung in der Suzuki-Miyaura-Reaktion. Dabei wurde neben der Untersuchung des Einflusses der Position der Phosphanylgruppe und der unterschiedlichen Substituenten ebenfalls die Auswirkung von elektronenziehenden und -schiebenden Gruppen am Phosphanrest untersucht. Die neutralen Mono- und Diphosphane wurden außerdem in der Kreuzkupplung von Arylhalogeniden und in der Synthese räumlich anspruchsvoller Biaryle verwendet. Des Weiteren wurden die (Phosphino)Imidazolium-Salze als Liganden in der Suzuki-Miyaura-Reaktion in ionischen Flüssigkeiten als Reaktionsmedium angewendet, um die Möglichkeit des Recyclings der Katalysatorphase zu untersuchen.:Table of Contents
Bibliographische Beschreibung und Referat ii
Präambel iii
Table of Contents 1
List of Abbreviations 5
A Introduction 9
1 Homogeneous Catalysis 9
2 References 11
B State of Knowledge 13
1 Transition Metal-Catalyzed C,C Cross-Coupling Reactions 13
2 Mizoroki-Heck Reaction 16
3 Suzuki-Miyaura Reaction 23
4 β-Oxopropyl Ester Synthesis 29
5 Ferrocenyl Phosphines in C,C Cross-Coupling Reactions 33
6 Phosphino Imidazoles and their Application in C,C Cross-Coupling Reactions 35
7 Motivation 36
8 References 37
C Metallocenyl Phosphine Palladium Dichlorides: Synthesis, Electrochemistry and their Application in C,C Coupling Reactions 44
1 Introduction 44
2 Results and Discussion 45
2.1 Ligand Synthesis and Properties 45
2.2 Electrochemistry 47
2.3 Single Crystal X-ray Structure Determination 51
2.4 Catalytic Investigations 55
2.4.1 Mizoroki-Heck Catalysis 55
2.4.2 Suzuki-Miyaura Catalysis 56
3 Conclusions 58
4 Experimental Section 60
4.1 General Data 60
4.2 Instruments 60
4.3 Electrochemistry 60
4.4 Spectro-electrochemistry 61
4.5 Materials 61
4.6 General Procedure for the Synthesis of Phosphines 3 and 6 61
4.7 General Procedure for the Synthesis of the Seleno Phosphines 4 and 7 65
4.8 General Procedure for the Synthesis of the Palladium Complexes 9a – e and 10a – d 69
4.9 General Procedure for the Mizoroki-Heck Reaction 72
4.10 General Procedure for the Suzuki-Miyaura Reaction 73
4.11 Crystal Data for 4b 73
5 Supporting Information 73
6 Acknowledgement 77
7 References 77
D Fundamental Study of (Ferrocenylethynyl)phosphines: Correlation of Steric and Electronic Effects in C,C Cross-Coupling Reactions 81
1 Introduction 81
2 Results and Discussion 82
2.1 Synthesis, Reaction Chemistry and Characterization 82
2.2 C,C Cross-Coupling Reactions 95
2.2.1 Suzuki-Miyaura Reaction 95
2.2.2 Mizoroki-Heck Reaction 96
3 Conclusions 97
4 Experimental Section 99
4.1 General Data and Materials 99
4.2 Instruments 99
4.3 Electrochemistry 100
4.4 Spectro-electrochemistry 100
4.5 General Procedure for the Synthesis of Phosphines 3b – f 101
4.6 General Procedure for the Synthesis of Seleno Phosphines 4b – f 104
4.7 General Procedure for the Synthesis of Palladium Complexes 6e, 6f and 7a – f 106
4.8 Synthesis of [PdCl2(P(C≡CFc)(Cy)2)2][B(C6F5)4]2 ([7f][(B(C6F5)4)]2) 110
4.9 General Procedure for the Suzuki-Miyaura Reaction 110
4.10 General Procedure for the Mizoroki-Heck Reaction 110
4.11 Crystal Structure Determination 111
5 Supporting Information 112
6 Acknowledgement 114
7 References 114
E (Ethynylferrocenyl)phosphine Ruthenium Complexes in Catalytic β-Oxopropyl Benzoate Formation 119
1 Introduction 119
2 Experimental Section 120
2.1 General Procedure and Materials 120
2.2 General Procedure for the Synthesis of Ruthenium Complexes 3a – 3e and 10 121
2.3 Synthesis of (Et2N)P(C≡C-PPh2)2 (6) 124
2.4 Synthesis of P(C≡CFc)(C≡CPPh2)2 (9) 124
2.5 Synthesis of (RuCl2(η6-p-cymene))(FcC≡C)P(C≡CPPh2(RuCl2(η6-p-cymene)))2 (10) 125
2.6 General Procedure for the Catalytic Reactions 125
2.7 Crystal Structure Determination 126
3 Results and Discussion 127
4 Conclusions 135
5 Supporting Information 135
6 Acknowledgement 135
7 References 136
F Phosphino Imidazoles and Imidazolium Salts for Suzuki-Miyaura C,C Coupling Reactions 138
1 Introduction 138
2 Results and Discussion 139
2.1 Synthesis 139
2.2 Characterization 143
2.3 Catalysis 148
3 Conclusions 152
4 Experimental Section 154
4.1 General Procedures 154
4.2 Synthesis of 1-(4-iodophenyl)-4,5-dimethyl-1H-imidazole (3b) 155
4.3 Synthesis of 1-(4-ferrocenylphenyl)-1H-imidazole (5) 156
4.4 Synthesis of 1-(4-(ethynylferrocenyl)phenyl)-1H-imidazole (7) 156
4.5 Synthesis of 1-(4-(1,1’-biphenyl))-4,5-dimethyl-1H-imidazole (9) 157
4.6 General Synthesis Procedure for Phosphines 11a – f 157
4.7 General Procedure for the Synthesis of Seleno Phosphines 11a-Se – f-Se 165
4.8 General Procedure for the Synthesis of Imidazolium Salts 16a – 16d 169
4.9 Synthesis of 1-phenyl-2-(diphenylphosphino)-3-n-octyl-4,5-dimethyl-1H-imidazolium hexafluorophosphate (17a) 171
4.10 Synthesis of 1-phenyl-2-(dicyclohexylphosphino)-3-n-octyl-4,5-dimethyl-1H-imidazolium hexafluorophosphate (17b) 172
4.11 Synthesis of [(1-(4-Br-C6H4)-cC3H2N2-3-n-Bu)2PdI2] (19) 173
4.12 Synthesis of 1-(4-(diphenylphosphino)phenyl)-3-n-octyl-4,5-dimethyl-1H-imidazolium hexafluorophosphate (20) 173
4.13 General Procedure for the Suzuki-Miyaura Reaction 174
4.14 General Procedure for the Suzuki-Miyaura Reaction in Ionic Liquids 175
4.16 General Procedure for the Synthesis of Sterically Hindered Biaryls 175
4.17 Crystal Structure Determination 176
5 Supporting Information 177
6 Acknowledgement 180
7 References 180
G Imidazole Phosphines: Synthesis, Reaction Chemistry and Their Use in Suzuki-Miyaura C,C Cross-Coupling Reactions 184
1 Introduction 184
2 Results and Discussion 185
2.1 Synthesis and Characterization of Phosphino Imidazoles and Metallamacrocycles 185
2.2 Suzuki-Miyaura C,C Cross-Coupling Reactions 193
3 Conclusions 196
4 Experimental Section 197
4.1 General Procedures 197
4.2 Synthesis of 1-(4-(diphenylphosphino)phenyl)-4,5-dimethyl-1H-imidazole (4a) 198
4.3 Synthesis of 1-(4-(dicyclohexylphosphino)phenyl)-4,5-dimethyl-1H-imidazole (4b) 199
4.4 General Synthesis Procedure for Phosphines 6a – f 199
4.5 Synthesis of [Pd(1-(4-PPh2-C6H4)-2-PFur2-4,5-Me2-1H-C3N2)Cl2]2 (8) 204
4.6 Synthesis of [Pt(dppf)(C≡C-C6H4-4-PPh2)2] (11) 204
4.7 Synthesis of [Pt(dppf)(C≡C-C6H4-4-PPh2)2PtCl2)]2 (13) 205
4.8 General Procedure for the Suzuki-Miyaura Reaction 205
4.9 General Procedure for the Suzuki-Miyaura Coupling of Aryl Chlorides 206
4.10 General Procedure for the Synthesis of Sterically Hindered Biaryls 206
4.11 Crystal Structure Determination 206
5 Acknowledgement 207
6 Supporting Information 208
7 References 208
H Summary 211
Acknowledgement/Dank 219
Publications, Oral Presentations, Poster 220
Publications 220
Oral Presentations 221
Posters 221
Curriculum Vitae 223
Selbstständigkeitserklärung 224
Appendix 225
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:19743 |
| Date | 09 July 2012 |
| Creators | Milde, Bianca |
| Contributors | Lang, Heinrich, Spange, Stefan, Technische Universität Chemnitz |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | doc-type:doctoralThesis, info:eu-repo/semantics/doctoralThesis, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
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