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Catalytic activation of H2 under mild conditions by an [FeFe]-hydrogenase model via an active μ-hydride species
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
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2013 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 135, no 37, 13688-13691 p.Article in journal (Refereed) Published
Abstract [en]

A [FeFe]-hydrogenase model (1) containing a chelating diphosphine ligand with a pendant amine was readily oxidized by Fc+ (Fc = Cp 2Fe) to a FeIIFeI complex ([1]+), which was isolated at room temperature. The structure of [1]+ with a semibridging CO and a vacant apical site was determined by X-ray crystallography. Complex [1]+ catalytically activates H2 at 1 atm at 25 C in the presence of excess Fc+ and P(o-tol) 3. More interestingly, the catalytic activity of [1]+ for H2 oxidation remains unchanged in the presence of ca. 2% CO. A computational study of the reaction mechanism showed that the most favorable activation free energy involves a rotation of the bridging CO to an apical position followed by activation of H2 with the help of the internal amine to give a bridging hydride intermediate.

Place, publisher, year, edition, pages
2013. Vol. 135, no 37, 13688-13691 p.
Keyword [en]
Activation free energy, Apical positions, Bridging hydride, Catalytic activation, Computational studies, Diphosphine ligand, Reaction mechanism, Room temperature
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-133266DOI: 10.1021/ja408376tISI: 000330163000020ScopusID: 2-s2.0-84884498203OAI: diva2:660640
Knut and Alice Wallenberg Foundation

QC 20140224

Available from: 2013-10-30 Created: 2013-10-29 Last updated: 2014-05-26Bibliographically approved
In thesis
1. Theoretical Studies on Water Splitting Using Transition Metal Complexes
Open this publication in new window or tab >>Theoretical Studies on Water Splitting Using Transition Metal Complexes
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. xii, 66 p.
TRITA-BIO-Report, ISSN 1654-2312 ; 2014:6
National Category
Theoretical Chemistry
urn:nbn:se:kth:diva-145191 (URN)978-91-7595-069-3 (ISBN)
Public defence
2014-06-13, Albanova FB53, Roslagstullsbacken 21, Stockholm, 10:00 (English)

QC 20140526

Available from: 2014-05-26 Created: 2014-05-14 Last updated: 2014-05-26Bibliographically approved

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