Electron-Transfer-Catalyzed Rearrangement of Unsymmetrically Substituted Diiron Dithiolate Complexes Related to the Active Site of the [FeFe]-Hydrogenases

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• 作者：Salah Ezzaher ; Jean-Fran&ccedil ; ois Capon ; Fré ; dé ; ric Gloaguen ; Fran&ccedil ; ois Y. Pé ; tillon ; Philippe Schollhammer ; Jean Talarmin
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：November 12, 2007
• 年：2007
• 卷：46
• 期：23
• 页码：9863 - 9872
• 全文大小：229K
• 年卷期：v.46,no.23(November 12, 2007)
• ISSN：1520-510X

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.