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Issue 23, 2017
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Electrocatalytic proton reduction by a model for [NiFeSe] hydrogenases

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Abstract

Two new heterodinuclear nickel–iron complexes [Ni(pbSmSe)FeCpCO]PF6 and [Ni(xbSmSe)FeCpCO]PF6 were synthesized as mimics of the [NiFeSe] hydrogenase active site (HCp = cyclopentadiene; H2pbSmSe = 1,9-diselenol-3,7-dithia-2,2,8,8-tetramethylnonane; H2xbSmSe = 1,2,-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene). The compounds were characterized by single crystal X-ray diffraction and cyclic voltammetry. X-ray structure determinations showed that in both NiFe complexes the nickel(II) center is in a square-planar S2Se2 environment; the two selenolate donors are bridging to the iron(II) center that is further coordinated to an η5-cyclopentadienyl group and a carbon monoxide ligand. Electrochemical studies showed that the complex [Ni(pbSmSe)FeCpCO]PF6 is an electrocatalyst for the production of H2 in DMF in the presence of acetic acid at −2.1 V vs. Fc+/Fc; a foot-of-the-wave (FOWA) analysis of the catalytic currents yielded an estimation of kobs of 24 s−1.

Graphical abstract: Electrocatalytic proton reduction by a model for [NiFeSe] hydrogenases

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Publication details

The article was received on 17 Mar 2017, accepted on 24 May 2017 and first published on 25 May 2017


Article type: Paper
DOI: 10.1039/C7DT00972K
Citation: Dalton Trans., 2017,46, 7506-7514
  • Open access: Creative Commons BY-NC license
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    Electrocatalytic proton reduction by a model for [NiFeSe] hydrogenases

    G. Gezer, D. Durán Jiménez, M. A. Siegler and E. Bouwman, Dalton Trans., 2017, 46, 7506
    DOI: 10.1039/C7DT00972K

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