Electron-transfer-catalyzed rearrangement of unsymmetrically substituted diiron dithiolate complexes related to-the active site of the [FeFe]-Hydrogenases

被引：101

作者：

Ezzaher, Salah ^{[1
]}

Capon, Jean-Francois ^{[1
]}

Gloaguen, Frederic ^{[1
]}

Petillon, Francois Y. ^{[1
]}

Schollhammer, Philippe ^{[1
]}

Talarmin, Jean ^{[1
]}

机构：

[1] Univ Bretagne Occidentale, UFR Sci & Tech, CNRS, UMR Chim Electrochim Mol & Chim Analyt 6521, F-29238 Brest 3, France

来源：

INORGANIC CHEMISTRY | 2007年 / 46卷 / 23期

关键词：

D O I：

10.1021/ic701327w

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Novel asymmetrically substituted azadithiolate compounds [Fe-2(CO)(4)(kappa(2)-dppe){mu-SCH2N(R)CH2S}] (R = Pr-i, 1a; CH2CH2OCH3, 1b; CH2C6H5, 1c) have been synthesized by treatment of [Fe-2(CO)(6)(mu-adt)] [adt = SCH2N(R)CH2S, with R = Pr-i, CH2CH2OCH3, CH2C6H5] with dppe (dppe = Ph2PCH2CH2PPh2) in refluxing toluene in the presence of Me3NO. la-c have been characterized by single-crystal X-ray diffraction analyses. The electrochemical investigation of 1a-c and of [Fe-2(CO)(4)(kappa(2)-dppe)(mu-pdt)] (1d) [pdt = S(CH2)(3)S] in MeCN- and THF-[NBu4][PF6] has demonstrated that the electrochemical reduction of 1a-d gives rise to an Electron-transfer-catalyzed (ETC) isomerization to the symmetrical isomers 2a-d where the dppe ligand bridges the iron centers. Compounds 2a-d were characterized by IR and NMR spectroscopy, elemental analysis, and X-ray crystallography for 2a.

引用

页码：9863 / 9872

页数：10

共 89 条

[1] Models of the iron-only hydrogenase:: Reactions of [Fe2(CO)6(μ-pdt)] with small bite-angle diphosphines yielding bridge and chelate diphosphine complexes [Fe2(CO)4(diphosphine)(μ-pdt)] [J].