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)Fe^II(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-Se_Ph-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-S_Ph-Fe-S complex; treatment with O-abstraction agents such as P(o

SUBMITTER: Yang X 

PROVIDER: S-EPMC6354737 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature