The Siamese-Twin Porphyrin and its Metal Complexes: Platforms for Multi-Electron Redox Chemistry

by Anastasia Vogel
Doctoral thesis
Date of Examination:2016-10-21
Date of issue:2017-02-14
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Ulf Diederichsen
Persistent Address: http://dx.doi.org/10.53846/goediss-6119

 

 

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Abstract

English

This work comprises a redox-chemical investigation of a pyrazole-containing expanded porphyrin - the so-called Siamese-twin porphyrin. It includes synthetic organic and inorganic work and applies a series of analytical techniques. Repeated periphery-to-core fusion reactions of the ligand framework upon oxidation were studied in detail. Further, communication of the porphyrin-like hemi-macrocycles in a monopalladium(II) complex were revealed. Redox investigations and complementary calculations were performed to uncover the importance of a metalation-induced tautomerism on the electronic structure of the expanded porphyrin. Additional cooperative effects of the non-innocent ligands system and its central ion in bimetallic manganese(III) complexes were examined.
Keywords: expanded porphyrins; oxidation; macrocycles; manganese; palladium; aromaticity
 
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