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Electronic Structure and Reactivity of Bioinspired Organometallic Iron Complexes Relevant to Small Molecule Activation

dc.contributor.advisorMeyer, Franc Prof. Dr.
dc.contributor.authorKupper, Claudia Gisela
dc.publisherNiedersächsische Staats- und Universitätsbibliothek Göttingende
dc.titleElectronic Structure and Reactivity of Bioinspired Organometallic Iron Complexes Relevant to Small Molecule Activationde
dc.contributor.refereeMeyer, Franc Prof. Dr.
dc.description.abstractengThis PhD thesis focuses on the development and characterization of new organometallic iron complexes as models for abundant enzymatic systems. The use of a macrocyclic tetracarbene ligand system results in novel features of the organometallic iron complexes compared to literature-known nitrogen-coordinated model compounds. In particular, the strong σ-donating carbene donors induce a destabilization of the d(x²−y²) orbital and thus an increased HOMO−LUMO gap in the oxoiron(IV) complex studied in this thesis. This makes the high-valent oxoiron(IV) compound a unique system which is able to activate weak C–H bonds via the triplet pathway only. Moreover, mixed-valent and high-valent µ-nitridodiiron systems are developed and their properties are studied by a series of analytical techniques including x-ray diffraction and Mössbauer spectroscopy. Furthermore, a complete series of structurally characterized {FeNO}6–8 species is presented. Using a variety of spectroscopic and theoretical methods, the redox processes within this series are identified as largely metal centered. Finally, initial studies toward the development of new hybrid ligand systems combining N-donating and C-donating groups are
dc.contributor.coRefereeFeussner, Ivo Prof. Dr.
dc.contributor.thirdRefereeAckermann, Lutz Prof. Dr.
dc.contributor.thirdRefereeSchneider, Sven Prof. Dr.
dc.contributor.thirdRefereeSiewert, Inke Prof. Dr.
dc.contributor.thirdRefereeDemir, Selvan Prof. Dr.
dc.subject.engorganometallic chemistryde
dc.subject.engN-heterocyclic carbene ligandsde
dc.subject.engoxoiron complexesde
dc.subject.engC–H activationde
dc.subject.engnitric oxidede
dc.subject.engiron-nitrosyl complexesde
dc.subject.engMössbauer spectroscopyde
dc.affiliation.instituteFakultät für Chemiede
dc.subject.gokfullChemie  (PPN62138352X)de

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