Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Theoretical Insights into Heme Catalysed Oxidation of Cyclohexane to Adipic Acid 
Stockholm University, Faculty of Science, Department of Physics. (Per E.M. Siegbahn; Margareta Blomberg)
Stockholm University, Faculty of Science, Department of Physics. (Per E.M. Siegbahn; Margareta Blomberg)
Stockholm University, Faculty of Science, Department of Physics. (Per E.M. Siegbahn; Margareta Blomberg)
Stockholm University, Faculty of Science, Department of Physics. (Per E.M. Siegbahn; Margareta Blomberg)
Show others and affiliations
(English)Article in journal (Refereed) Submitted
Abstract [en]

Adipic acid is a key compound in the chemical industry, where it is mainly used in the production of polymers. The conventional process of its generation requires vast amounts of energy, and moreover, pro- duces environmentally deleterious substances. Thus, there is interest in alternative ways to gain adequate amounts of adipic acid. Experimental reports on a one-pot iron catalyzed conversion of cyclohexane to adipic acid motivated a theoretical investigation based on DFT calculations. The process investigated is interesting because it requires less energy than contemporary methods and does not produce environmentally harmful side products. The aim of the present contribution is to gain insight into the mechanism of the iron catalyzed cyclohexane conversion to provide a basis for further development of this process. The rate limiting step along the reaction path is discussed. Furthermore, it is shown that the C-C bond breaks spontaneously after an initial hydrogen atom abstraction from one of the cylohexane-1,2-diol hydroxides.

Keyword [en]
adipic acid, dft, iron porphyrin, oxidation
National Category
Organic Chemistry
Research subject
Chemical Physics
Identifiers
URN: urn:nbn:se:su:diva-38202OAI: oai:DiVA.org:su-38202DiVA: diva2:307162
Available from: 2010-03-31 Created: 2010-03-31 Last updated: 2010-04-01Bibliographically approved
In thesis
1. Biomimetic Iron Complexes involved in Oxygenation and Chlorination: A Theoretical Study
Open this publication in new window or tab >>Biomimetic Iron Complexes involved in Oxygenation and Chlorination: A Theoretical Study
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

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.
Keyword
biomimetic, iron, density functional theory, intradiol, chlorination, adpic acid, diamond core, reactivity
National Category
Inorganic Chemistry Theoretical Chemistry
Research subject
Chemical Physics
Identifiers
urn:nbn:se:su:diva-38197 (URN)978–91–7447–013–0 (ISBN)
Public defence
2010-04-30, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
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.Available from: 2010-04-08 Created: 2010-03-31 Last updated: 2010-04-07Bibliographically approved

Open Access in DiVA

No full text

Search in DiVA

By author/editor
Noack, HolgerValentin, GeorgievBlomberg, Margareta R.A.Siegbahn, Per E,M.
By organisation
Department of Physics
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

urn-nbn

Altmetric score

urn-nbn
Total: 196 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf