文摘
Novel asymmetrically substituted azadithiolate compounds [Fe2(CO)4(2-dppe){-SCH2N(R)CH2S}] (R = iPr, 1a;CH2CH2OCH3, 1b; CH2C6H5, 1c) have been synthesized by treatment of [Fe2(CO)6(-adt)] [adt = SCH2N(R)CH2S,with R = iPr, CH2CH2OCH3, CH2C6H5] with dppe (dppe = Ph2PCH2CH2PPh2) in refluxing toluene in the presenceof Me3NO. 1a-c have been characterized by single-crystal X-ray diffraction analyses. The electrochemical investigationof 1a-c and of [Fe2(CO)4(2-dppe)(-pdt)] (1d) [pdt = S(CH2)3S] in MeCN- and THF-[NBu4][PF6] has demonstratedthat the electrochemical reduction of 1a-d gives rise to an Electron-transfer-catalyzed (ETC) isomerization to thesymmetrical isomers 2a-d where the dppe ligand bridges the iron centers. Compounds 2a-d were characterizedby IR and NMR spectroscopy, elemental analysis, and X-ray crystallography for 2a.
