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Issue 5, 2019

Oxygen uptake in complexes related to [NiFeS]- and [NiFeSe]-hydrogenase active sites

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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.

Graphical abstract: Oxygen uptake in complexes related to [NiFeS]- and [NiFeSe]-hydrogenase active sites

Supplementary files

Article information


Submitted
05 Oct 2018
Accepted
04 Nov 2018
First published
05 Nov 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 1368-1373
Article type
Edge Article

Oxygen uptake in complexes related to [NiFeS]- and [NiFeSe]-hydrogenase active sites

X. Yang, L. C. Elrod, J. H. Reibenspies, M. B. Hall and M. Y. Darensbourg, Chem. Sci., 2019, 10, 1368 DOI: 10.1039/C8SC04436H

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