Biomimetic Iron Complexes involved in Oxygenation and Chlorination : A Theoretical Study

• Main Author: Noack, Holger
• Format: Doctoral Thesis
• Language: English
• Published: Stockholms universitet, Fysikum 2010
• Subjects: biomimetic; iron; density functional theory; intradiol; chlorination; adpic acid; diamond core; reactivity; Bio-inorganic chemistry; Bio-oorganisk kemi; Theoretical chemistry; Teoretisk kemi
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-38197; http://nbn-resolving.de/urn:isbn:978–91–7447–013–0

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 iron-oxo 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. === At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted. Paper 2: Accepted. Paper 3: Submitted.