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Enhancing the Catalytic Activity of a Biomimetic Diiron Complex by the Introduction of a Water Molecule as a Coordinating Lewis Base-Mechanistic Insights from Theoretical Modeling.
Stockholm University, Faculty of Science, Department of Physics.
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Manuscript (Other academic)
URN: urn:nbn:se:su:diva-25473OAI: diva2:199790
Part of urn:nbn:se:su:diva-8197Available from: 2008-09-15 Created: 2008-09-15 Last updated: 2010-01-13Bibliographically approved
In thesis
1. Biomimetic Transition Metal Catalysts: Insights from Theoretical Modeling
Open this publication in new window or tab >>Biomimetic Transition Metal Catalysts: Insights from Theoretical Modeling
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The scientific interest in the chemistry of synthetic transition metal complexes is motivated by at least two arguments:

1.These can be regarded as models of biological transition metal complexes, e.g. metalloenzymes, whose functions can be difficult to reveal in detail due to their complexity.

2.Transition metal complexes are used for catalytic purposes in the industrial synthesis of chemicals. There is a large potential for further development of this technology, which can be motivated both by economic and environmental arguments.

In the present thesis, density functional theory (a quantum mechanical method) has been applied to model reactions involving synthetic iron and copper complexes in solution. The complexity of the solvent environment is a challenging problem for theoretical investigations and a significant part of the theses has been to investigate the mechanistic effects of metal-coordinating solvent molecules, Lewis bases and counter ions. For example, it is explained why the cleavage of the O-O bond in heme-diiron-peroxides is faster in the presence of a coordinating Lewis base. Furthermore, the experimentally observed structure-activity relationship between the Fe(III)(µ-O)2Fe(IV) and (H2O)Fe(III)(µ-O)Fe(IV)O motifs is given an explanation. In addition, the present thesis presents a systematic investigation of how the self-interaction error in density functional theory (DFT) affects the modeling of transition metal catalysis.

Place, publisher, year, edition, pages
Stockholm: Fysikum, 2008. 150 p.
Catalysis, biomimetic, copper, non-heme iron, heme iron, O2 cleavage, H-atom transfer, radical chemistry, redox chemistry, thermo chemistry, entropy calculations, quantum chemistry, spin states, density functional theory (DFT), self-interaction error (SIE).
National Category
Atom and Molecular Physics and Optics
Research subject
Chemical Physics
urn:nbn:se:su:diva-8197 (URN)9789171557223 (ISBN)
Public defence
2008-09-19, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Available from: 2008-09-15 Created: 2008-09-15Bibliographically approved

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