Reaction of Aryl Diazonium Salts and Diiron(I) Dithiolato Carbonyls: Evidence for Radical Intermediates

摘要

Treatment of Fe2(pdt)(CO)4(dppv) (>1) with aryldiazonium salts affords the 34e⁻ adducts [Fe2(pdt)(μ-N2Ar)(CO)4(dppv)]⁺ (pdt²⁻ = 1,3-propanedithiolate, dppv = cis-C2H2(PPh2)2). Under some conditions, the same reaction gave substantial amounts of [>1]⁺, the product of electron-transfer. Consistent with the influence of electron transfer in the reactions of some electrophiles with Fe(I)Fe(I) dithiolates, the reaction of [Me3S2]⁺ and Fe2(pdt)(CO)4(dppbz) was found to give [Fe2(pdt)(CO)4(dppbz)]⁺ as well as Me2S and Me₂S₂ (dppbz = 1,2-bis(diphenylphosphino)benzene).