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二硫代和氢桥联(CO/CN)Fe-Ni 配合物,具有未保护的 CN:[Ni-Fe]氢化酶活性位点的[Ni-R]态模型。

A Dithiolato and Hydrido Bridged (CO/CN)Fe-Ni Complex with Unprotected CN: A Model for the [Ni-R] State of the [Ni-Fe] Hydrogenase Active Site.

机构信息

Department of Chemistry, Graduate School of Science and Research Center for Materials Science , Nagoya University , Furo-Cho, Chikusa-ku, Nagoya 464-8602 , Japan.

Institute of Transformative Bio-Molecules (WPI-ITbM) , Nagoya University , Furo-Cho, Chikusa-ku, Nagoya 464-8601 , Japan.

出版信息

Inorg Chem. 2020 Jan 21;59(2):968-971. doi: 10.1021/acs.inorgchem.9b03082. Epub 2019 Dec 31.

Abstract

A dithiolate/hydride bridged Fe-Ni complex, [(CN)(CO)Fe(μ-pdt)(μ-H)Ni(CN)(PCy)] (, pdt = propane-1,3-dithiolate) has been synthesized by the reaction of [(CN)(CO)Fe(pdt)] with [Ni(Cl)(H)(PCy)] as a synthetic analogue of the Ni-R state of the active site of the [Ni-Fe] hydrogenase. X-ray crystallography of this model complex suggests that the hydride unsymmetrically binds to Ni and Fe similar to natural [Ni-Fe] hydrogenases.

摘要

一种二硫醇/氢桥联的 Fe-Ni 配合物,[(CN)(CO)Fe(μ-pdt)(μ-H)Ni(CN)(PCy)](,pdt = 丙烷-1,3-二硫醇)已通过[(CN)(CO)Fe(pdt)]与[Ni(Cl)(H)(PCy)]的反应合成,作为 [Ni-Fe]氢化酶活性位点的 Ni-R 状态的合成类似物。该模型配合物的 X 射线晶体学表明,氢化物不对称地与 Ni 和 Fe 键合,类似于天然 [Ni-Fe]氢化酶。

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