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

Treatment of Fe(2)(pdt)(CO)(4)(dppv) (1) with aryldiazonium salts affords the 34e(-) adducts [Fe(2)(pdt)(μ-N(2)Ar)(CO)(4)(dppv)](+) (pdt(2-) = 1,3-propanedithiolate, dppv = cis-C(2)H(2)(PPh(2))(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 [Me(3)S(2)](+) and Fe(2)(pdt)(CO)(4)(dppbz) was found to give [Fe(2)(pdt)(CO)(4)(dppbz)](+) as well as Me(2)S and Me(2)S(2) (dppbz = 1,2-bis(diphenylphosphino)benzene).