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

Schiewer, Christine Elisabeth

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

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Fakultät für Chemie (inkl. GAUSS) [701]

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