Biomimetic Iron Complexes involved in Oxygenation and Chlorination: A Theoretical Study
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
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.
Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University , 2010. , a-d, viii, 75 p.
biomimetic, iron, density functional theory, intradiol, chlorination, adpic acid, diamond core, reactivity
Inorganic Chemistry Theoretical Chemistry
Research subject Chemical Physics
IdentifiersURN: urn:nbn:se:su:diva-38197ISBN: 978–91–7447–013–0OAI: oai:DiVA.org:su-38197DiVA: diva2:306951
2010-04-30, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Kaupp, Martin, Professor
Blomberg, Margareta R. A., ProfessorSiegbahn, Per E. M., Professor
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted.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.2010-04-082010-03-312010-04-07Bibliographically approved
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