Catalytic activation of H2 under mild conditions by an [FeFe]-hydrogenase model via an active μ-hydride species
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
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 (+), which was isolated at room temperature. The structure of + with a semibridging CO and a vacant apical site was determined by X-ray crystallography. Complex + 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 + 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.
Activation free energy, Apical positions, Bridging hydride, Catalytic activation, Computational studies, Diphosphine ligand, Reaction mechanism, Room temperature
IdentifiersURN: urn:nbn:se:kth:diva-133266DOI: 10.1021/ja408376tISI: 000330163000020ScopusID: 2-s2.0-84884498203OAI: oai:DiVA.org:kth-133266DiVA: diva2:660640
FunderKnut and Alice Wallenberg Foundation
QC 201402242013-10-302013-10-292014-05-26Bibliographically approved