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Oxygen Uptake in Complexes Related to [NiFeS] and [NiFeSe] Hydrogenase Active Sites

Abstract

A biomimetic study for S/Se oxygenation in Ni(µ-EPh)(µ-SN2)Fe, (E = S or Se; SN2= Me-diazacycloheptane-CH2CH2S) ; Fe = (η5-C5H5)FeII(CO)) complexes related to the oxygen-damaged active sites of [NiFeS]/[NiFeSe]-H2ases is described. Mono- and di-oxygenates (major and minor species, respectively) of the chalcogens result from exposure of the heterobimetallics to O2; one was isolated and structurally characterized to have Ni-O-SePh-Fe-S connectivity within a 5-membered ring. A compositionally analogous mono-oxy species was implicated by ν(CO) IR spectroscopy to be the corresponding Ni-O-SPh-Fe-S complex; treatment with O-abstraction agents such as P(o-tolyl)3 or PMe3 remediated the O damage. Computational studies (DFT) found that the lowest energy isomers of mono-oxygen derivatives of Ni(µ-EPh)(µ-SN2)Fe complexes were those with O attachment to Ni rather than Fe, a result consonant with experimental findings, but at odds with oxygenates found in oxygen-damaged [NiFeS]/[NiFeSe]-H2ase structures. A computer-generated model based on substituting -SMe for the N-CH2CH2S- sulfur donor of the N2S suggested that constraint within the chelate hindered O-atom uptake at that sulfur site.

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Publication details

The article was received on 05 Oct 2018, accepted on 04 Nov 2018 and first published on 05 Nov 2018


Article type: Edge Article
DOI: 10.1039/C8SC04436H
Citation: Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
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    Oxygen Uptake in Complexes Related to [NiFeS] and [NiFeSe] Hydrogenase Active Sites

    X. Yang, L. C. Elrod, J. Reibenspies, M. B. Hall and M. Y. Darensbourg, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C8SC04436H

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