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

by Claudia Gisela Kupper
Doctoral thesis
Date of Examination:2017-04-25
Date of issue:2017-06-15
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Ivo Feussner
Referee:Prof. Dr. Lutz Ackermann
Referee:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Inke Siewert
Referee:Prof. Dr. Selvan Demir
Persistent Address: http://dx.doi.org/10.53846/goediss-6340

 

 

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Abstract

English

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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