dc.contributor.advisor | Meyer, Franc Prof. Dr. | |
dc.contributor.author | Schiewer, Christine Elisabeth | |
dc.date.accessioned | 2018-05-02T09:04:36Z | |
dc.date.available | 2018-08-22T22:50:05Z | |
dc.date.issued | 2018-05-02 | |
dc.identifier.uri | http://hdl.handle.net/11858/00-1735-0000-002E-E3D3-F | |
dc.identifier.uri | http://dx.doi.org/10.53846/goediss-6855 | |
dc.language.iso | eng | de |
dc.publisher | Niedersächsische Staats- und Universitätsbibliothek Göttingen | de |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | |
dc.subject.ddc | 540 | de |
dc.title | Nitric Oxide Reactivity and Unusual Redox Properties of Biomimetic Iron-Sulfur Clusters with Alternative Cluster Ligands | de |
dc.type | doctoralThesis | de |
dc.contributor.referee | Meyer, Franc Prof. Dr. | |
dc.date.examination | 2018-02-23 | |
dc.description.abstracteng | This work describes the nitrosylation of biomimetic [2Fe–2S] clusters with phenylbis(benzimidazol-2-yl)methane or benzimidazolthiophenol ligands in different iron oxidation states and ligand protonation states. Mixed-valent clusters are oxidized to diferric clusters in the presence of nitric oxide before they further react to form dinitrosyl iron complexes (DNICs). The reaction was monitored by UV-vis and IR spectroscopy and the reaction products were characterized by X-ray diffraction, EPR, and Mössbauer spectroscopy. Protonation studies of the DNICs supported by DFT calculations were possible due to proton-responsive ligand sites on the benzimidazole moiety and they revealed significant IR spectroscopic changes for the NO ligands. Furthermore, a cubane-type [4Fe–4S] cluster is presented in which the coordination number of one iron atom depends on the counterion according to X-ray crystallography and Mössbauer spectroscopy. Oxidation of the cluster was studied by a series of analytical techniques indicating a similar change of the coordination number. Finally, 5,6-Dithia-1,10-phenanthroline was investigated as potential ligand for [2Fe–2S] clusters. As shown in electrochemical experiments, the ligand can be employed as disulfide/dithiol switch. A proton induced shift of the reductive wave was seen in cyclic voltammetry and the S–S bond cleavage mechanism switches from EEC to ECE(C). | de |
dc.contributor.coReferee | Tittmann, Kai Prof. Dr. | |
dc.contributor.thirdReferee | Siewert, Inke Prof. Dr. | |
dc.contributor.thirdReferee | Demir, Selvan Prof. Dr. | |
dc.contributor.thirdReferee | Thomas, Franziska Dr. | |
dc.contributor.thirdReferee | Otte, Matthias Dr. | |
dc.subject.eng | bioinorganic chemistry | de |
dc.subject.eng | iron-sulfur clusters | de |
dc.subject.eng | nitric oxide | de |
dc.subject.eng | dinitrosyl iron complexes | de |
dc.subject.eng | DNIC | de |
dc.subject.eng | disulfide/dithiol switch | de |
dc.identifier.urn | urn:nbn:de:gbv:7-11858/00-1735-0000-002E-E3D3-F-9 | |
dc.affiliation.institute | Fakultät für Chemie | de |
dc.subject.gokfull | Chemie (PPN62138352X) | de |
dc.description.embargoed | 2018-08-22 | |
dc.identifier.ppn | 102227192X | |