C-Cl Bond Activation at Rotated vs Unrotated Dinuclear Site Related to [FeFe]-Hydrogenases

被引：2

作者：

Chatelain, Lucile ^{[1
]}

Arrigoni, Federica ^{[2
]}

Schollhammer, Philippe ^{[1
]}

Zampella, Giuseppe ^{[2
]}

机构：

[1] Univ Bretagne Occidentale, UMR CNRS Chim Electrochim Mol & Chim Analyt 6521, F-29238 Brest, France

[2] Univ Milano Bicocca, Dept Biotechnol & Biosci, I-20126 Milan, Italy

来源：

INORGANIC CHEMISTRY | 2023年 / 62卷 / 51期

关键词：

ACTIVE-SITE; REDUCTIVE DECHLORINATION; OXIDATIVE ADDITION; METHYLENE-CHLORIDE; SYNTHETIC MODELS; TERMINAL HYDRIDE; H-2; REACTIVITY; COMPLEXES; DICHLOROMETHANE;

D O I：

10.1021/acs.inorgchem.3c03481

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The novel dinuclear complex related to the [FeFe]-hydrogenases active site, [Fe-2(mu-pdt)(kappa(2)-dmpe)(2)(CO)(2)] (1), is highly reactive toward chlorinated compounds CHxCl4-x (x = 1, 2) affording selectively terminal or bridging chloro diiron isomers through a C-Cl bond activation. DFT calculations suggest a cooperative mechanism involving a formal concerted regioselective chloronium transfer depending on the unrotated or rotated conformation of two isomers of 1.

引用

页码：20913 / 20918

页数：6

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