Towards unravelling the mechanism of copper-catalyzed cyclopropanation:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Abschlussarbeit Buch |
| Sprache: | English |
| Veröffentlicht: |
2000
|
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | 382 S. Ill., graph. Darst. : 30 cm |
Internformat
MARC
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| 044 | |a gw |c DE | ||
| 049 | |a DE-355 |a DE-29T |a DE-83 |a DE-188 | ||
| 100 | 1 | |a Straub, Bernd Franz |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Towards unravelling the mechanism of copper-catalyzed cyclopropanation |c [vorgelegt von Bernd Franz Straub] |
| 264 | 1 | |c 2000 | |
| 300 | |a 382 S. |b Ill., graph. Darst. : 30 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 502 | |a Heidelberg, Univ., Diss., 2000 | ||
| 650 | 7 | |a Hochschulschrift |2 gtt | |
| 650 | 0 | 7 | |a Katalyse |0 (DE-588)4029921-1 |2 gnd |9 rswk-swf |
| 650 | 0 | 7 | |a Cyclopropanierung |0 (DE-588)4221170-0 |2 gnd |9 rswk-swf |
| 650 | 0 | 7 | |a Kupferkomplexe |0 (DE-588)4223142-5 |2 gnd |9 rswk-swf |
| 655 | 7 | |0 (DE-588)4113937-9 |a Hochschulschrift |2 gnd-content | |
| 689 | 0 | 0 | |a Cyclopropanierung |0 (DE-588)4221170-0 |D s |
| 689 | 0 | 1 | |a Katalyse |0 (DE-588)4029921-1 |D s |
| 689 | 0 | 2 | |a Kupferkomplexe |0 (DE-588)4223142-5 |D s |
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| 943 | 1 | |a oai:aleph.bib-bvb.de:BVB01-009338535 | |
Datensatz im Suchindex
| _version_ | 1812460893237149696 |
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TABLE OF CONTENTS
1 GOAL OF THE THESIS
1
2 SUMMARY
2
3 DIAZOALKANE CHEMISTRY OF PLATINUM
12
3.1 A-CARBONYL DIAZOALKANE TRANSITION METAL COMPLEXES -
12
AN INTRODUCTION
3.2 DEGENERATE REARRANGEMENT OF PLATINUM DIAZOALKANE
COMPLEX 2 18
3.3 REACTIVITY OF THE DIAZOALKANE COMPLEX 2 AND ITS
DERIVATIVES 23
3.4 CONCLUSIONS FROM PLATINUM DIAZOALKANE CHEMISTRY 26
4 COPPER(L) DIPHOSPHINOMETHANE COMPLEXES
28
4.1 INTRODUCTION 28
4.1.1 D
10-D10 INTERACTIONS - A SHORT SURVEY 28
4.1.2 COPPER(L) COMPLEXES WITH CHELATING DIPHOSPHINE LIGANDS 30
4.1.3 COPPER(L) FLUORIDES AND HIGH FLUORINE COORDINATION NUMBERS 32
4.2 D
10-D10 INTERACTIONS IN A DINUCLEAR COPPER(L) DICATION 34
4.3 THE FIRST TRIGONAL PLANAR P
3-FLUORIDO COPPER(L)
COMPLEX
37
4.4 STRUCTURE OF A P
3-FLUORIDO TRICOPPER(L) DICATION:
A DENSITY FUNCTIONAL STUDY
41
4.5 REACTIVITY OF COPPER DIPHOSPHINOMETHANE COMPLEXES
TOWARDS DIAZOALKANES 49
BIBLIOGRAFISCHE INFORMATIONEN
HTTP://D-NB.INFO/960757856
5
5.1
5.2
5.3
5
.
3.1
5
.
3.2
5.4
5
.
4.1
5
.
4.2
5
.
4.3
5
.
4.4
5
.
4.5
5
.
4.6
5.5
COPPER(L) OLEFIN CHEMISTRY
COINAGE METAL OLEFIN COMPLEXES -AN INTRODUCTION
LIGAND DESIGN: FROM THEORY TO EXPERIMENT
A COPPER(L) ETHYLENE IMINOPHOSPHANAMIDE COMPLEX
SYNTHESIS, STRUCTURE, SPECTROSCOPY, AND BONDING OF THE ETHYLENE
COMPLEX 15
COPPER(L) OLEFIN BOND STRENGTH: A DENSITY FUNCTIONAL STUDY
COPPER(L) OLEFIN COMPLEXES: STRUCTURES AND DYNAMICS
PREPARATIVE STRATEGIES TOWARDS COPPER(L) IMINOPHOSPHANAMIDE
COMPLEXES
THE NORBORNENE COMPLEX 21
THE STYRENE COMPLEX 24
THE MALEIC ANHYDRIDE COMPLEX 26
THE 1,4-BENZOQUINONE COMPLEX 29
THE DIMETHYL BUTYNEDIOATE COMPLEX 31
COMPARISON OF COMPUTED AND EXPERIMENTAL COPPER(L)
OLEFIN BOND STRENGTHS
50
50
58
64
64
70
78
78
80
86
91
100
111
118
THE FIRST NEUTRAL BIS(P-OXO)DICOPPER
COMPLEX
COPPER DIOXYGEN CHEMISTRY - AN INTRODUCTION
SYNTHESIS, STRUCTURE, AND SPECTROSCOPY OF
BIS(P-OXO)DICOPPER( III) COMPLEX 33
STRUCTURE OF THE CU
202 CORE: A DENSITY FUNCTIONAL
STUDY
DECOMPOSITION BEHAVIOR OF BIS(|U-OXO)DICOPPER(LLL)
COMPLEX 33
A HYPOTHESIS ON THE OXIDATION MECHANISM INVOLVING
TYPE 3 ENZYMES
120
120
130
135
138
141
7 COPPER-CATALYZED CYCLOPROPANATION 144
7.1 INTRODUCTION 144
7.1.1 THE MECHANISM OF COPPER-CATALYZED CYCLOPROPANATION 144
7.1.2 TRANSITION METAL A-CARBONYL CARBENE COMPLEXES 151
7.1.3 D
10-ML3 COMPLEXES WITH A CARBENE, SILYLENE OR STANNYLENE
LIGAND
157
7.2 THE FIRST DIAZOALKANE COPPER COMPLEX 36
161
7.3 THE PATHWAY TO COPPER(L) CARBENES 175
7.4 ELECTRONIC STRUCTURES OF COPPER CARBENES: A DENSITY
FUNCTIONAL STUDY 190
7.5 SUBSTITUENT EFFECTS IN COPPER(L) CARBENE MODEL
COMPLEXES
196
7.6 WOLFF-TYPE REARRANGEMENTS: A DENSITY FUNCTIONAL
STUDY 201
7.7 COMPUTING NMR CHEMICAL SHIFTS FOR COPPER(L)
CARBENE COMPLEXES
206
7.8 CYCLOPROPANATION BY COPPER CARBENES 208
7.9 THE SYNTHESIS OF THE FIRST COPPER(L) CARBENE
COMPLEXES: SPECTROSCOPY, REACTIVITY, AND STABILITY 219
7.9.1 CATALYTIC CYCLOPROPANATION WITH COPPER ETHYLENE COMPLEX 15
221
.
7.9.2
IN SITU
SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF THE FIRST
D
10-ML3 TYPE COPPER(L) CARBENE 56 223
7.9.3 COPPER CARBENE COMPLEX 58 / 235
7.9.4 COPPER CARBENE COMPLEX 60 239
7.9.5 THE ELECTRONIC STRUCTURE OF COPPER(L) CARBENES DERIVED FROM
NMR SPECTROSCOPY 246
7.10 GENERAL MECHANISTIC CONCLUSIONS FOR THE
COPPER-CATALYZED CYCLOPROPANATION REACTION 248
8 OUTLOOK
253
III
9 EXPERIMENTAL SECTION
9.1 GENERAL PROCEDURES
9.2 STARTING MATERIALS
9.2
.1 SYNTHESIS OF DI-F-BUTYLCHLORPHOSPHANE (IMPROVED PROCEDURE)
9.2.2 SYNTHESIS OF P,P-DI-/-BUTYL-X
3-PHOSPHANAMIDE
9.2.3 SYNTHESIS OF P,P-DI-/-BUTYL-N-(TRIMETHYLSI!YLH
3-PHOSPHANAMIDE
9.2.4 SYNTHESIS OF P,P-DI-F-BUTYL-N,N'-BIS(TRIMETHYLSILYL)IMINO-A,
5-
PHOSPHANAMIDE (14)
9.3 COPPER(L) DIPHOSPHINOMETHANE COMPLEXES
9.3
.1 SYNTHESIS OF [CU2(MTBPM)2]2+[(PF6) ]2, (112+)[(PF6)-]2 AND
[CU
2(MTBPM)2]2+[(03SCF3)-]2) (112+)[(03SCF3)']2
9.3.2 SYNTHESIS OF [CU
3(P3-F)(^DTBPM)3]2+[(03SCF3)-]2, (122+)[(OTF)]2
AND [CU
3(P3-F)(|U-DTBPM)3]2+[(PF6)-]2, (122+)[(PF6)']2
9.4 IMINOPHOSPHANAMIDE COPPER CHEMISTRY
9.4
.1 SYNTHESIS OF [FBU2P(NSIME3)2-K2A/]CU(TI2-C2H4) (15)
9.4.2 SYNTHESIS OF [FBU
2P(NSIME3)2-K2/V]CU(R12-C7HIO) (21)
9.4.3 SYNTHESIS OF [FBU
2P(NSIME3)2-K2/V]CU(R|2-C6H5C2H3) (24)
9.4.4 SYNTHESIS OF [FFIU
2P(NSIME3)2-K2/V]CU[R12-C2H2(C0)20] (26)
9.4.5 SYNTHESIS OF [FBU
2P(NSIME3)2-K2A/]CU[RI2-1,4-C6H402] (29)
9.4.6 SYNTHESIS OF [FBU
2P(NSIME3)2-K2/V]CU[TI2-C2(C02ME)2] (31)
9.4.7 SYNTHESIS OF [U
2P(NSIME3)2-K2A/]2CU2(P-0)2 (33)
9
.4.8 SYNTHESIS OF [FBU2P(NSIME3)2-K2/V]CU[0(N2)C2(CI2H8)-K0:K/V]
(36)
9.4.9 SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF
[FBU
2P(NSIME3)2-K2A/]CU=C(C02ME)PH (56)
9.4.10 SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF
[FBU
2P(NSIME3)2-K2/Y)CU=C[C02CH(4-C6H5CI]PH (58)
9.4.1
1 SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF
[FBU
2P(NSIME3)2-K2A/JCU=C[C02/PR]CI4HG (60)
257
257
259
260
261
262
263
264
264
266
268
268
269
271
272
274
275
276
278
280
281
282
IV
10 X-RAY DIFFRACTION DATA 283
10.1 [(DTBPM)R{ 7
2-CH(C02ME)2}]+ [BFYY]', (8*) [BFYY]' 283
10.2 [CU
2(P-DTBPM)2F[(03SCF3)-]2L (112*)[(OTF)]2 286
10.3 [CU
3(P
3
-F)(N-DTBPM)3F [(PF6)-]
2
, (122*)[(PFS)12 288
10.4 [CU
3(P3-F)(|X-DTBPM)3]2*[(03SCF3)L2, (122T)[(OTF) ]2 293
10.5 [FBU
2P(NSIME3)2-K2A/]CU(RI2-C2H4) (15) 298
10.6 [FFIUZPFNSIMEAK-^NLCUTT^-CTH,,,) (21) 300
10.7 [(BU
2P(NSIME3)2-K2N]CU[I12-H2C2(C0)20](26) 304
10.8 [BU
2P(NSIME3)2-K2A/]CU[R|2-C2(C02ME)2] (31) 308
10.9 [(BU
2P(NSIME3)2-K2N]2CU2(P-0)2] (34) 310
10.10 [U
2P(NSIME3)2-K2N]CU[0(N2)C2(CI2HE)-
KW:K0] 0(N
2)C2(C12H8) (36-35) 313
11 COMPUTATIONAL PROCEDURES
316
11.1 METHODS 316
11.1.1 LAN L2DZ BASIS SET 317
11.1.2 3-21G . 320
11.1.3 6-31 G(D) 321
11.1.4 6-311+G(2D,P) 322
11.1.5 6-311+G(3DF,3PD) 325
11.2 COMPUTATIONAL DATA
Y 327
11.3 COMPUTATION OF NMR CHEMICAL SHIFTS 351
12 ABBREVIATIONS AND NOMENCLATURE
353
12.1 ABBREVIATIONS 353
12.2 NOMENCLATURE 356
V
13
REFERENCES
358
14 ACKNOWLEDGEMENT
369
CURRICULUM VITAE
370
NUMBERING OF THE COMPOUNDS AND
COMPUTED STRUCTURES
375
VI |
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| indexdate | 2024-10-09T18:10:02Z |
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| language | English |
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| spelling | Straub, Bernd Franz Verfasser aut Towards unravelling the mechanism of copper-catalyzed cyclopropanation [vorgelegt von Bernd Franz Straub] 2000 382 S. Ill., graph. Darst. : 30 cm txt rdacontent n rdamedia nc rdacarrier Heidelberg, Univ., Diss., 2000 Hochschulschrift gtt Katalyse (DE-588)4029921-1 gnd rswk-swf Cyclopropanierung (DE-588)4221170-0 gnd rswk-swf Kupferkomplexe (DE-588)4223142-5 gnd rswk-swf (DE-588)4113937-9 Hochschulschrift gnd-content Cyclopropanierung (DE-588)4221170-0 s Katalyse (DE-588)4029921-1 s Kupferkomplexe (DE-588)4223142-5 s DE-604 DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=009338535&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Straub, Bernd Franz Towards unravelling the mechanism of copper-catalyzed cyclopropanation Hochschulschrift gtt Katalyse (DE-588)4029921-1 gnd Cyclopropanierung (DE-588)4221170-0 gnd Kupferkomplexe (DE-588)4223142-5 gnd |
| subject_GND | (DE-588)4029921-1 (DE-588)4221170-0 (DE-588)4223142-5 (DE-588)4113937-9 |
| title | Towards unravelling the mechanism of copper-catalyzed cyclopropanation |
| title_auth | Towards unravelling the mechanism of copper-catalyzed cyclopropanation |
| title_exact_search | Towards unravelling the mechanism of copper-catalyzed cyclopropanation |
| title_full | Towards unravelling the mechanism of copper-catalyzed cyclopropanation [vorgelegt von Bernd Franz Straub] |
| title_fullStr | Towards unravelling the mechanism of copper-catalyzed cyclopropanation [vorgelegt von Bernd Franz Straub] |
| title_full_unstemmed | Towards unravelling the mechanism of copper-catalyzed cyclopropanation [vorgelegt von Bernd Franz Straub] |
| title_short | Towards unravelling the mechanism of copper-catalyzed cyclopropanation |
| title_sort | towards unravelling the mechanism of copper catalyzed cyclopropanation |
| topic | Hochschulschrift gtt Katalyse (DE-588)4029921-1 gnd Cyclopropanierung (DE-588)4221170-0 gnd Kupferkomplexe (DE-588)4223142-5 gnd |
| topic_facet | Hochschulschrift Katalyse Cyclopropanierung Kupferkomplexe |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=009338535&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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