New class of diiron dithiolates related to the Fe-only hydrogenase active site:: Synthesis and characterization of [Fe2(SR)2(CNMe)7]2+

被引：64

作者：

Lawrence, JD ^{[1
]}

Rauchfuss, TB ^{[1
]}

Wilson, SR ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA

来源：

INORGANIC CHEMISTRY | 2002年 / 41卷 / 24期

关键词：

D O I：

10.1021/ic025919t

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Electron-rich polyisocyano derivatives Fe-2(S2CnH2n)(CO)(6-x)(CNMe)(x) (x similar to 4) undergo oxidatively induced (FeCp2+) reaction with additional CNMe to give [Fe-2(SR)(2)(CNMe)(7)](PF6)(2), a new class of iron thiolates. Crystallographic characterization established that the 34 e(-) dinuclear core resembles the oxidized (H-2-binding) form of the active sites of the Fe-only hydrogenases, key features being the face-sharing bioctahedral geometry, the mu-CX ligand, and an Fe-Fe separation of 2.61 Angstrom. Oxidation of the phenylthiolate Fe-2(Sph)(2)(CO)(2)(CNMe)(4) led to mononuclear [Fe(SPh)(CNMe)(5)](PF6), which is analogous to [Fe-2(SR)(2)(CNMe)(10)](PF6)(2) formed upon treatment of [Fe-2(S2C3H6)(CNMe)(7)](PF6)(2) with excess CNMe.

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页码：6193 / 6195

页数：3

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