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

von Claudia Gisela Kupper
Dissertation
Datum der mündl. Prüfung:2017-04-25
Erschienen:2017-06-15
Betreuer:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Ivo Feussner
Gutachter:Prof. Dr. Lutz Ackermann
Gutachter:Prof. Dr. Sven Schneider
Gutachter:Prof. Dr. Inke Siewert
Gutachter:Prof. Dr. Selvan Demir
Zum Verlinken/Zitieren: http://dx.doi.org/10.53846/goediss-6340

 

 

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Zusammenfassung

Englisch

This 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 described.
Keywords: organometallic chemistry; N-heterocyclic carbene ligands; oxoiron complexes; C–H activation; kinetics; nitric oxide; iron-nitrosyl complexes; Mössbauer spectroscopy
 
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