Issue 5, 2019

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
05 okt 2018
Accepted
04 noy 2018
First published
05 noy 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 1368-1373

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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