| Abstract
| - Novel asymmetrically substituted azadithiolate compounds [Fe2(CO)4(κ2-dppe){μ-SCH2N(R)CH2S}] (R = iPr, 1a;CH2CH2OCH3, 1b; CH2C6H5, 1c) have been synthesized by treatment of [Fe2(CO)6(μ-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(κ2-dppe)(μ-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.
- The electrochemical reduction of four unsymmetrical [Fe2(CO)4(κ2-dppe)(μ-dithiolate)] complexes (1), including the novel derivatives where the dithiolate bridge is SCH2N(R)CH2S (R = iPr, CH2CH2OMe, CH2Ph), triggers an electron-transfer-catalyzed rearrangement to the symmetrical isomers, 2.
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