Bioinspired Dinuclear Copper Complexes for Oxygen Activation

by Martin Alfred Dzemski
Doctoral thesis
Date of Examination:2022-09-29
Date of issue:2022-12-06
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Inke Siewert
Persistent Address: http://dx.doi.org/10.53846/goediss-9599

 

 

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Abstract

English

This thesis explores new bioinspired bimetallic copper complexes for the activation of dioxygen. Therefore, two novel TACN/pyrazolate ligand scaffolds with reduced steric hindrance were introduced and successfully established. The important primary reactive dioxygen adducts, such as the peroxido, hydroperoxido and superoxido species of the corresponding dinuclear copper complexes, were synthesized and studied by UV/vis spectroscopy. Moreover, the decomposition of the µ-1,2-peroxo dicopper(II) complexes were studied at different temperatures. These experiments allowed the determination of the activation energies for the decomposition reactions. Additionally, the interaction of the new cupric peroxides with Lewis acids like lithium and calcium ions were investigated by UV/vis titration experiments. Reactivity studies were also performed with the reactive oxygen adducts. Initial results regarding the oxygen reduction reaction are presented and discussed in this work.
Keywords: transition metal complex; bimetallic complex; oxygen activation; copper complexes; coordination chemistry; dinuclear complex; uv/vis spectroscopy; resonance raman spectroscopy