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Structural and Kinetic Studies of Intermediates of a Biomimetic Diiron Proton-Reduction Catalyst
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.ORCID iD: 0000-0001-7919-2444
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.ORCID iD: 0000-0003-0216-6920
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.ORCID iD: 0000-0002-9933-9084
2018 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 57, no 2, p. 768-776Article in journal (Refereed) Published
Abstract [en]

One-electron reduction and subsequent protonation of a biomimetic proton-reduction catalyst [FeFe(μ-pdt)(CO)6] (pdt = propanedithiolate), 1, were investigated by UV-vis and IR spectroscopy on a nano- to microsecond time scale. The study aimed to provide further insight into the proton-reduction cycle of this [FeFe]-hydrogenase model complex, which with its prototypical alkyldithiolate-bridged diiron core is widely employed as a molecular, precious metal-free catalyst for sustainable H2 generation. The one-electron-reduced catalyst was obtained transiently by electron transfer from photogenerated [Ru(dmb)3]+ in the absence of proton sources or in the presence of acids (dichloro- or trichloroacetic acid or tosylic acid). The reduced catalyst and its protonation product were observed in real time by UV-vis and IR spectroscopy, leading to their structural characterization and providing kinetic data on the electron and proton transfer reactions. 1 features an intact (μ22-pdt)(μ-H)Fe2 core in the reduced, 1-, and reduced-protonated states, 1H, in contrast to the Fe-S bond cleavage upon the reduction of [FeFe(bdt)(CO)6], 2, with a benzenedithiolate bridge. The driving-force dependence of the rate constants for the protonation of 1- (kpt = 7.0 × 105, 1.3 × 107, and 7.0 × 107 M-1 s-1 for the three acids used in this study) suggests a reorganization energy >1 eV and indicates that hydride complex 1H is formed by direct protonation of the Fe-Fe bond. The protonation of 1- is sufficiently fast even with the weaker acids, which excludes a rate-limiting role in light-driven H2 formation under typical conditions.

Place, publisher, year, edition, pages
2018. Vol. 57, no 2, p. 768-776
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-343862DOI: 10.1021/acs.inorgchem.7b02687ISI: 000422810900029PubMedID: 29297686OAI: oai:DiVA.org:uu-343862DiVA, id: diva2:1187190
Funder
Swedish Research Council, 2016-04271Stiftelsen Olle Engkvist Byggmästare, 2016/3Available from: 2018-03-02 Created: 2018-03-02 Last updated: 2018-10-24Bibliographically approved
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Wang, ShihuaiAster, AlexanderLomoth, ReinerHammarström, Leif

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