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Nitric Oxide Reactivity and Unusual Redox Properties of Biomimetic Iron-Sulfur Clusters with Alternative Cluster Ligands

dc.contributor.advisorMeyer, Franc Prof. Dr.
dc.contributor.authorSchiewer, Christine Elisabeth
dc.publisherNiedersächsische Staats- und Universitätsbibliothek Göttingende
dc.titleNitric Oxide Reactivity and Unusual Redox Properties of Biomimetic Iron-Sulfur Clusters with Alternative Cluster Ligandsde
dc.contributor.refereeMeyer, Franc Prof. Dr.
dc.description.abstractengThis 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.coRefereeTittmann, Kai Prof. Dr.
dc.contributor.thirdRefereeSiewert, Inke Prof. Dr.
dc.contributor.thirdRefereeDemir, Selvan Prof. Dr.
dc.contributor.thirdRefereeThomas, Franziska Dr.
dc.contributor.thirdRefereeOtte, Matthias Dr.
dc.subject.engbioinorganic chemistryde
dc.subject.engiron-sulfur clustersde
dc.subject.engnitric oxidede
dc.subject.engdinitrosyl iron complexesde
dc.subject.engdisulfide/dithiol switchde
dc.affiliation.instituteFakultät für Chemiede
dc.subject.gokfullChemie  (PPN62138352X)de

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