p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Abschlussarbeit Buch |
| Sprache: | English |
| Veröffentlicht: |
Erlangen ; Nürnberg
[2017]
|
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis Inhaltsverzeichnis |
| Beschreibung: | V, 321 Seiten Illustrationen, Diagramme 21 cm |
Internformat
MARC
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| 245 | 1 | 0 | |a p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands |c vorgelegt von Stephan Pflock |
| 264 | 1 | |a Erlangen ; Nürnberg |c [2017] | |
| 300 | |a V, 321 Seiten |b Illustrationen, Diagramme |c 21 cm | ||
| 336 | |b txt |2 rdacontent | ||
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| 338 | |b nc |2 rdacarrier | ||
| 502 | |b Dissertation |c Friedrich-Alexander-Universität Erlangen-Nürnberg |d 2017 | ||
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Datensatz im Suchindex
| _version_ | 1804178390943531008 |
|---|---|
| adam_text | C
ONTENTS
1 INTRODUCTION AND STATE OF KNOWLEDGE 1
1.1 THE HISTORY OF HOMO- AND HETEROSCORPIONATE L IGANDS
.................................
2
1.1.1 TRIS(PYRAZOL-L-YL) BO RA TE S
.................................................................. 2
1.1.2
TRIS(PYRAZOL-L-YL)METHANES...............................................................
5
1.1.3 BIS (PYRAZOL-L-YL) ACETIC A CID
S............................................................ 5
1.2 COORDINATION CHEMISTRY OF BIS(PYRAZOL-L-YL)ACETIC ACIDS AND RELATED
LIGANDS 11
1.2.1 ENZYME
MODELING..............................................................................
11
1.2.2 CARBONYL C OM
PLEXES........................................................................
13
1.2.3 FURTHER TRANSITION METAL COMPLEXES WITH BIS(PYRAZOL-L-YL)ACETIC
A
CIDS.......................................................................................................
15
1.2.4 TIN AND GALLIUM COMPLEXES WITH CP AND SCORPIONATE LIGANDS . . . 17
1.3 THE DYE-SENSITISED SOLAR C E L L
.........................................................................
21
1.3.1 THE 2-SCHEME IN
PHOTOSYNTHESIS...................................................... 21
1.3.2 WORKING PRINCIPLE OF A DSSC
............................................................. 23
1.3.3 ROLE OF THE ELECTROLYTE IN D S S C S
................................................... 24
1.4 MEDICAL APPLICATIONS OF COMPLEXES WITH MULTIDENTATE LIGANDS AND
METAL-
LODRUGS................................................................................................................
28
1.4.1 CO-RELEASING M
OLECULES..................................................................
29
1.4.2 RADIOPHARMACEUTICALS
.........................................................................
31
1.4.3 THE SUPEROXIDE DISMUTASE AND MANGANESE SOD M IM E TIC S
..........
34
1.5 DISTORTION INDICIES AND CORRELATION TO THE SPIN STATE OF A COMPLEX
METAL ION 37
2 OBJECTIVES AND AIMS 39
3 RESULTS AND DISCUSSION 43
3.1 SYNTHESIS, CHARACTERISATION AND STERIC MAPS OF BIS (PYRAZOL-L-YL)
ACETIC ACIDS 44
3.1.1 PREPARATION OF AN ETHYL-SUBSTITUTED BIS (PYRAZOL-L-YL) ACETIC ACID
. . 44
3.1.2 PREPARATION OF A PHENYL-SUBSTITUTED BIS (PYRAZOL-L-YL) ACETIC ACID
. . 46
3.1.3 CALCULATION OF BURIED VOLUMES AND STERIC MAPS OF BIS(PYRAZOL-L-
YL) ACETIC ACIDS
.....................................................................................
49
3.2 SYNTHESIS AND CHARACTERISATION OF TRANSITION METAL COMPLEXES WITH
HBPZA 56
3.3 DETERMINATION OF A RUTHENIUM(IV)-OXIDO SPECIES BY CRYOSPRAY ESI-TOF
MS 68
3.4 SYNTHESIS AND CHARACTERISATION OF TRANSITION METAL COMPLEXES BEARING
B D M P Z A
..............................................................................................................
74
3.4.1 SYNTHESIS, CHARACTERISATION AND OXIDATION OF CHROMIUM(II) COM
PLEXES BEARING B D M P
ZA.........................................................................
74
3.4.2 PREPARATION OF DIVALENT COMPLEXES CONTAINING A MANGANESE, IRON,
COBALT OR NICKEL CENTRE
......................................................................
81
3.4.3 PREPARATION OF TRIVALENT COMPLEXES CONTAINING A MANGANESE, IRON,
OR COBALT C E N TR E
..................................................................................
86
3.4.4 MAGNETIC PROPERTIES OF BDMPZA
COMPLEXES........................................ 90
3.4.5 SPECTROSCOPIC AND ELECTROCHEMICAL PROPERTIES OF BDMPZA COMPLEXES
92
3.4.6 S O LU B ILITY
..............................................................................................
96
3.5 PREPARATION OF CARBONYL COMPLEXES CONTAINING BDEPZA OR BDPPZA
LIGANDS 98
3.5.1 SYNTHESIS OF THE MANGANESE AND RHENIUM COMPLEXES [M (BDEPZA)
(CO)S]
AND [M(BDPPZA) (C O
)S].........................................................................
98
3.5.2 SYNTHESIS OF [R
U
(L)C1(CO)2] WITH HBDEPZA AND HBDPPZA ...... 106
3.6 SYNTHESIS AND CHARACTERISATION OF TRANSITION METAL COMPLEXES WITH
HBDEPZA 114
3.7 SYNTHESIS AND CHARACTERISATION OF TRANSITION METAL COMPLEXES WITH
HBDPPZA 124
3.8 SYNTHESIS AND CHARACTERISATION OF A MANGANESE COMPLEX WITH FOUR
BDBPZA
LIGANDS
................................................................................................................
134
3.9 STRUCTURAL INVESTIGATIONS OF BIS(PYRAZOL-L-YL)ACETATO COMPLEXES
...................
138
3.10 SOD ACTIVITY OF MANGANESE COMPLEXES BEARING BIS(PYRAZOL-1 -Y
1)ACETIC ACIDS 142
3.11 PREPARATION OF P-BLOCK METAL COMPLEXES BEARING BPZA OR BDMPZA
LIGANDS 147
3.11.1 SYNTHESIS OF TIN(II) AND TIN(IV) COMPLEXES WITH BPZA AND BDMPZA
147
3.11.2 SYNTHESIS OF A GALLIUM(III) COMPLEX WITH BDM
PZA..............................158
4 SUMMARY 163
5 ZUSAMMENFASSUNG 177
6 EXPERIMENTAL SECTION 191
6.1 GENERAL R E M A RK
S................................................................................................
192
6.1.1 GENERAL SAFETY PRECAUTIONS FOR THE HANDLING OF PERCHLORATE SALTS .
. 192
6.1.2 WORKING TECHNIQUES
..............................................................................
192
6.1.3 INSTRUM
ENTATION........................................................................................192
6.1.4 C HEM
ICALS.................................................................................................196
6.2 SYNTHESIS OF C OM
POUNDS.................................................................................
199
6.2.1 SYNTHESIS OF BIS(PYRAZOL-L-YL)ACETIC A CIDS
.........................................
199
6.2.1.1 BIS(3,5-DIETHYLPYRAZOL- 1-YL)METHANE (HBDEPZM; 1) .... 199
6.2.1.2 BIS(3,5-DIETHYLPYRAZOL-L-YL)ACETIC ACID (HBDEPZA; 2) . . . 200
6.2.1.3 BIS(3,5-DIPHENYLPYRAZOL-L-YL)METHANE (HBDPPZM; 3) . . . 201
6.2.1.4 BIS(3,5-DIPHENYLPYRAZOL- 1-YL)ACETIC ACID (HBDPPZA; 4) . . 202
6.2.2 SYNTHESIS OF DIVALENT TRANSITION METAL COMPLEXES WITH HBPZA . . .
204
6.2.2.1 TRANS-[CR(BPZA)2] ( 5 )
........................................................... 204
6.2.2.2 CTS-[MN(BPZA)2] ( 6 )
.............................................................. 205
6.2.2.3 [MN(BPZA)2(H20)] ( 7 )
........................................................ 206
6.2.2.4 TRONS-[FE(BPZA)2] ( 8 )
........................................................... 207
6.2.2.5 M-[CO(BPZA)2] ( 9 )
.............................................................. 208
6.2.2.6 CIS-[NI(BPZA)2] (10) 209
6.2.2.7 RANS-[CU(BPZA)2] ( 1 1 )
........................................................
210
6.2.2.8 CT S-[ZN(BPZA)2] (12)
...............................................................211
6.2.3 SYNTHESIS OF DIVALENT AND TRIVALENT TRANSITION METAL COMPLEXES
WITH H B D M P Z A
.....................................................................................212
6.2.3.1 [CR(BDMPZA)2] (1 3 )
..............................................................
212
6.2.3.2 [CR(BDMPZA)2]BF4 (14)
.........................................................213
6.2.3.3 [CR(BDMPZA)2]PF6 (15)
.........................................................214
6.2.3.4 CIS-[CR(BDMPZA)2]BPH4 (1 6 )
...............................................
215
6.2.3.5 [MN(BDMPZA)2] ( 1 7 )
...........................................................
216
6.2.3.6 [FE(BDMPZA)2] ( 1 8 )
..............................................................
217
6.2.3.7 [CO(BDMPZA)2] (19)
...............................................................218
6.2.3.8 [NI(BDMPZA)2] ( 2 0 )
..............................................................
219
6.2.3.9 [MN(BDMPZA)2]BF4 ( 2 1 )
.....................................................
220
6.2.3.10 [FE(BDMPZA)2]BF4 (22) 221
6.2.3.11 [CO(BDMPZA)2]BF4 ( 2 3 )
..................................................... 222
6.2.4 SYNTHESIS OF CARBONYL COMPLEXES WITH HBDEPZA AND HBDPPZA . . . 224
6.2.4.1 [MN(BDEPZA) (CO)3] ( 2 4 )
.....................................................
224
6.2.4.2 [RE(BDEPZA) (CO)3] ( 2 5 )
.....................................................
225
6.2.4.3 [MN(BDPPZA) (CO)3] (2 6 )
.....................................................
226
6.2.4.4 [RE(BDPPZA) (CO)3] ( 2 7 )
.....................................................
227
6.2.4.5 [RU(BDEPZA)CL(CO)2] ( 2 8 )
..................................................
229
6.2.4.6 [RU(BDPPZA)CL(CO)2] (2 9 )
.................................
230
6.2.4.7 CRYSTALLISATION OF [RU(BDPPZA)(/I2-CL)(CO)]2 ( 3 0 )
..........
231
6.2.4.8 CRYSTALLISATION OF [RU(/Z2-0-BDPPZA)CL(C0)]2 (31) .... 232
6.2.5 SYNTHESIS OF DIVALENT TRANSITION METAL COMPLEXES WITH HBDEPZA . .
233
6.2.5.1 [MN(BDEPZA)2] (3 2 )
.................................................................
233
6.2.5.2 [FE(BDEPZA)2] ( 3 3 )
.................................................................
234
6.2.5.3 [CO(BDEPZA)2] ( 3 4 )
.................................................................
235
6.2.5.4 [NI(BDEPZA)2] ( 3 5 )
.................................................................
236
6.2.5.5 [CU(BDEPZA)2] ( 3 6 )
.................................................................
237
6.2.5.6 [ZN(BDEPZA)2] ( 3 7 )
................................................................. 238
6.2.6 SYNTHESIS OF DI- AND TRIVALENT TRANSITION METAL COMPLEXES WITH
HBDPPZA AND H B D FP Z A
...........................................................................
239
6.2.6.1 [CR(BDPPZA)2] ( 3 8 )
................................................................. 239
6.2.6.2 [MN(BDPPZA)2] (39) 240
6.2.6.3 [FE(BDPPZA)2] ( 4 0 )
................................................................ 241
6.2.6.4 [CO(BDPPZA)2] ( 4 1 )
...................................................................
242
6.2.6.5 [ZN(BDPPZA)2] ( 4 2 )
................................................................. 243
6.2.6.6 [FE(BDPPZA)2]BF4 ( 4 3 )
........................................................... 244
6.2.6.7 [MN(BDBPZA)2(H20 ) 3]2 (44) 245
6.2.7 SYNTHESIS OF P-BLOCK METAL COMPLEXES WITH BIS(PYRAZOL-L-YL)ACETIC
A
CIDS..................................................................................
246
6.2.7.1 [SN(BPZA)2] (45)
.................................................................... 246
6.2.7.2 [SN(BDMPZA)2] (4 6
)................................................................. 247
6.2.7.3 [SN(BDMPZA)F3] ( 4 7 )
.............................................................. 248
6.2.7.4 [GA(BDMPZA)2]C104 (4 8
).......................................................... 249
6.3 COMPUTATIONAL D E TA ILS
........................................................................................
251
6.3.1 BURIED VOLUMES AND STERIC M A P S
.........................................................251
6.3.2 CALCULATIONS REGARDING THE CIS-TRANS ISOMERISM IN [M(BPZA)2] COM
PLEXES
......................................................................................................
251
6.3.3 CALCULATION OF THE SN COMPLEXES IN THE OXIDATION STATES II, III
AND IV251
APPENDIX 253
A DETAILS OF STRUCTURE DETERM
INATIONS...................................................................254
B LIST OF C OM
POUNDS..............................................................................................
275
C ABBREVIATIONS AND SYMBOLS
...............................................................................277
D BALL AND STICK AND SPACE-FILLING PRESENTATION OF THE SYSTEMS [ZN(L)2]
AND
[ZN(L)CL]
.............................................................................................................283
E SOD ACTIVITY PLOTS OF [MN(BDEPZA)2] (32) AND [MN(BDPPZA)2] (39) ....
288
F STRUCTURAL DATA OF BIS(PYRAZOL-L-YL)ACETATO C O M P LEX ES
.................................
289
BIBLIOGRAPHY 291
DANKSAGUNG
315
PUBLICATIONS AND CONFERENCE CONTRIBUTIONS
319
|
| any_adam_object | 1 |
| author | Pflock, Stephan |
| author_facet | Pflock, Stephan |
| author_role | aut |
| author_sort | Pflock, Stephan |
| author_variant | s p sp |
| building | Verbundindex |
| bvnumber | BV044864600 |
| ctrlnum | (OCoLC)1044748664 (DE-599)DNB1152104489 |
| discipline | Chemie / Pharmazie |
| format | Thesis Book |
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| indexdate | 2024-07-10T08:03:13Z |
| institution | BVB |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-030259179 |
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| physical | V, 321 Seiten Illustrationen, Diagramme 21 cm |
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| spelling | Pflock, Stephan Verfasser aut p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands vorgelegt von Stephan Pflock Erlangen ; Nürnberg [2017] V, 321 Seiten Illustrationen, Diagramme 21 cm txt rdacontent n rdamedia nc rdacarrier Dissertation Friedrich-Alexander-Universität Erlangen-Nürnberg 2017 Übergangsmetallkomplexe (DE-588)4131837-7 gnd rswk-swf Komplexe (DE-588)4133953-8 gnd rswk-swf p-Element (DE-588)4667254-0 gnd rswk-swf Essigsäurederivate (DE-588)4153056-1 gnd rswk-swf (DE-588)4113937-9 Hochschulschrift gnd-content Übergangsmetallkomplexe (DE-588)4131837-7 s Essigsäurederivate (DE-588)4153056-1 s DE-604 p-Element (DE-588)4667254-0 s Komplexe (DE-588)4133953-8 s B:DE-101 application/pdf http://d-nb.info/1152104489/04 Inhaltsverzeichnis DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=030259179&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Pflock, Stephan p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands Übergangsmetallkomplexe (DE-588)4131837-7 gnd Komplexe (DE-588)4133953-8 gnd p-Element (DE-588)4667254-0 gnd Essigsäurederivate (DE-588)4153056-1 gnd |
| subject_GND | (DE-588)4131837-7 (DE-588)4133953-8 (DE-588)4667254-0 (DE-588)4153056-1 (DE-588)4113937-9 |
| title | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands |
| title_auth | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands |
| title_exact_search | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands |
| title_full | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands vorgelegt von Stephan Pflock |
| title_fullStr | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands vorgelegt von Stephan Pflock |
| title_full_unstemmed | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands vorgelegt von Stephan Pflock |
| title_short | p-block and transition metal complexes bearing bis(pyrazol-1-yl)acetato ligands |
| title_sort | p block and transition metal complexes bearing bis pyrazol 1 yl acetato ligands |
| topic | Übergangsmetallkomplexe (DE-588)4131837-7 gnd Komplexe (DE-588)4133953-8 gnd p-Element (DE-588)4667254-0 gnd Essigsäurederivate (DE-588)4153056-1 gnd |
| topic_facet | Übergangsmetallkomplexe Komplexe p-Element Essigsäurederivate Hochschulschrift |
| url | http://d-nb.info/1152104489/04 http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=030259179&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT pflockstephan pblockandtransitionmetalcomplexesbearingbispyrazol1ylacetatoligands |
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Inhaltsverzeichnis