Do S, S'-coordinated \(\it o\)-Dithiobenzosemiquinonate(1-) radicals exist in coordination compounds?
- Transition metal bound thiolates play essential roles in bioinorganic electron transfer and catalytic processes. Understanding the bonding between the sulfur and the metal atoms are important for gaining insight into the structural and functional relationship. The most studied are the bis(dithiolato)transition metal complexes. The hotly debated question is whether dithiolenes can act as innocent or non-innocent ligands. In this work an unambiguous assignment of the spectroscopic oxidation states of the ligand in a series of bis(3,5-di-\(\it tert\)-butylbenzodithiolate)-transition metal complexes has been done by a combination of crystallographic, spectroscopic (IR, resonance Raman, UV-vis, Mössbauer, EPR) and advanced computational (Relativistic DFT and \(\textit {ab initio}\)) methods. In particular, UV-Vis, Infrared, and resonance Raman spectroscopy are found to be of immense importance in the unequivocal detection of \(\it S,S\)-coordinated 1,2-dithiobenzosemiquinonate(1-) radicals in coordination compounds.
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| Author: | Kallol RayGND |
|---|---|
| URN: | urn:nbn:de:hbz:294-13937 |
| Subtitle (English): | A combined experimental and computational study |
| Referee: | Karl WieghardtGND, William S. SheldrickGND |
| Document Type: | Doctoral Thesis |
| Language: | English |
| Date of Publication (online): | 2005/08/11 |
| Date of first Publication: | 2005/08/11 |
| Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
| Granting Institution: | Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie |
| Date of final exam: | 2005/01/25 |
| Creating Corporation: | Fakultät für Chemie und Biochemie |
| GND-Keyword: | Übergangsmetall; Dithiolene; Thiylradikal; Spektroskopie / Marker; Ab-initio-Rechnung |
| Institutes/Facilities: | Max-Planck Institut für Bioanorganische Chemie, Mülheim an der Ruhr |
| Dewey Decimal Classification: | Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie |
| faculties: | Fakultät für Chemie und Biochemie |
| Licence (German): |  Keine Creative Commons Lizenz - es gelten der Veröffentlichungsvertrag und das deutsche Urheberrecht |
