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铁酰基配合物的合成与反应活性模拟 [Fe]-氢化酶活性中心。

Synthesis and reactivity of iron acyl complexes modeling the active site of [Fe]-hydrogenase.

机构信息

Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, SB-ISIC-LSCI, BCH 3305, Lausanne 1015, Switzerland.

出版信息

J Am Chem Soc. 2010 Jan 27;132(3):928-9. doi: 10.1021/ja9100485.

Abstract

A [Fe(II)Fe(II)] dithiolate complex containing acyl and carbonyl ligands was synthesized. The diiron complex reacted with phosphine, cyanide, isocyanide, and CO to give monomeric Fe(II) complexes reproducing the first coordination sphere of the active site of [Fe]-hydrogenase (H(2)-forming methylene-tetrahydromethanopterin dehydrogenase, Hmd) in various states. All the acyl and carbonyl carbons in the diiron complex underwent facile isotopic exchange with (13)CO via monomeric Fe tricarbonyl intermediates.

摘要

合成了一种含有酰基和羰基配体的[Fe(II)Fe(II)]二硫代配合物。该二铁配合物与膦、氰化物、异氰化物和 CO 反应,生成单体 Fe(II)配合物,以各种状态再现[Fe]-氢化酶(H2 形成亚甲基四氢叶酸脱氢酶,Hmd)活性部位的第一配位球。二铁配合物中的所有酰基和羰基碳都通过单体 Fe 三羰基中间体与(13)CO 进行了易于进行的同位素交换。

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