Electron-transfer-catalyzed rearrangement of unsymmetrically substituted diiron dithiolate complexes related to-the active site of the [FeFe]-Hydrogenases
Electron-transfer-catalyzed rearrangement of unsymmetrically substituted diiron dithiolate complexes related to-the active site of the [FeFe]-Hydrogenases
复制标题
DOI：
10.1021/ic701327w
复制
发表时间：
2007-11-12
影响因子：
4.6
通讯作者：
Talarmin, Jean
中科院分区：
文献类型：
--
作者：
Ezzaher, Salah;Capon, Jean-Francois;Talarmin, Jean
[Fe-2(CO)(6)(MU-ADT)][ADT=SCH_2N(R)CH_2S，R=Pr-I，1a；CH_2CH_2OCH_3，1b；CH_2C_6H_5，1c][ADT=SCH_2N(R)CH_2S，其中R=Pr-I，CH_2CH_2OCH3，CH_2C_6H_5]与dppe(dppe=Ph2PCH_2CH_2Ph_2)在Me3NO存在下回流甲苯合成了新的不对称取代氮杂二硫化合物[Fe-2(CO)(4)(kappa(2)-dppe){Mu-SCH_2N(R)CH_2S}](R=Pr-I；CH_2CH_2OCH3，CH_2C_6H_5)。用单晶X射线衍射法对La-C进行了表征。1a-c和[Fe-2(CO)(4)(kappa(2)-dppe)(mU-pdt)](1d)[pdt=S(CH2)(3)S]在MeCN-和THF-[NBu4][Pf6]中的电化学研究表明，1a-d的电化学还原导致电子转移催化(ETC)异构化为对称的异构体2a-d，其中dppe配体和桥联铁中心。化合物2a-d的结构经红外光谱、核磁共振光谱、元素分析和X-射线结晶学确证。
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.