Ph.D. Thesis: Biomimetic Iron Complexes involved in Oxygenation and Chlorination. A Theoretical Study
by
Holger Noack(Stockholm University, Department of Physics)
→
Europe/Stockholm
Magnélisalen, KÖL, Arrheniuslab.
Magnélisalen, KÖL, Arrheniuslab.
Kemiska övningslaboratoriet, Svante
Arrhenius väg 16 B
Description
Biomimetic chemistry is directed towards the simulation of enzymatic reactivity with synthetic
analogues. In this thesis a quantum chemical method has been employed to study the mechanism of
highly reactive iron-oxo complexes involved in oxygenation and chlorination of organic substrates.
The aim of this research is to gain greater understanding for the reactivity paradigm of the ironoxo
group.
One reaction deals with the conversion of cyclohexane into adipic acid, a key chemical in
industrial chemistry, catalyzed by an iron(II)-porphyrin complex in the presence of dioxygen. This
process constitutes a ’green’ alternative to conventional adipic acid production, and is thus of
great interest to synthetic chemistry. Another reaction investigated herein regards the selective
chlorination observed for a new group of non-heme iron enzymes. With help of theoretical
modeling it was possible to propose a mechanism that explains the observed selectivity. It is
furthermore demonstrated how a biomimetic iron complex simulates the enzymatic reactivity by
a different mechanism.
Other topics covered in this thesis regard the structure-reactivity relationship of a binuclear iron
complex and the intradiol C-C bond cleavage of catechol catalyzed by an iron(III) complex.
