Bioinspirierte Sauerstoffaktivierung an Bis(benzimidazolyl)basierten Kupfer(I)komplexen und Spektroskopische Studien an Bis(benzoxazolyl) Kupfer(II)-Verbindungen

Bioinspired Bis(benzimidazole)based Copper(I) Complexes and Spectroscopic Studies at Bis(benzoxazole) Copper(II) Compounds

by Anna Kölpin
Doctoral thesis
Date of Examination:2021-02-23
Date of issue:2021-05-04
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Inke Siewert
Referee:Prof. Dr. Dietmar Stalke
Referee:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Nathalie Kunkel
Referee:Dr. Christian Sindlinger
Persistent Address: http://dx.doi.org/10.53846/goediss-8589

 

 

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Abstract

English

The active sites of type III copper proteins (i.e. tyrosinase) provide inspiration for the development of copper complexes for the activation of O2 as well as for catalytic oxidation and oxygenation reactions of CH substrates. These reactions often proceed via highly reactive CuII2(μ-η2:η2-peroxo) (P) or CuIII2(μ-oxo)2 (O) intermediates. Consequently, the preparation of these intermediates and a comparison of their reactivity are important aspects of bioinorganic Cu/O2 chemistry. We recently introduced bis(benzimidazole) based ligands for bioinspired Cu/O2 chemistry, and we showed that these ligands are potentially proton-responsive. This allowed for the reversible interconversion between P and O intermediates by (de)protonation to occur s at the ligand periphery, which may be biologically relevant in pH-dependent protonation state changes of histidine ligands in metalloproteins. The second part of this work, the synthesis of bis(benzoxazole) copper(II) compounds was described and the complexes were characterized by several analytical techniques including NMR, UV-vis, IR spectroscopies as well as cyclic voltammetry and spectroelectrochemistry. In the future, obtained homoleptic copper(II) complexes might be used as redox mediators in dye sensitized solar solar cells.
Keywords: Bionarganic chemistry, Copper, O-O activation, UV-vis, paramagnetic NMR,electrochemistry, spectroelectrochemistry, dye sensitized solar cells, redox mediator
 
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