Adding Diversity to Diiron Aminocarbyne Complexes with Amine Ligands

The reactions of the diiron aminocarbyne complexes [Fe2Cp2(NCMe)(CO)(mu-CO){mu-CN(Me)(R)}]CF3SO3 (R = Me, 1a(NCMe); R = Cy, 1b(NCMe)), freshly prepared from the tricarbonyl precursors 1a-b, with primary amines containing an additional function (i.e., alcohol or ether) proceeded with the replacement of the labile acetonitrile ligand and formation of [Fe2Cp2(NH2CH2CH2OR')(CO)(mu-CO){mu-CN(Me)(R)}]CF3SO3 (R = Me, R' = H, 2a; R = Cy, R' = H, 2b; R = Cy, R' = Me, 2c) in 81-95% yields. The diiron-oxazolidinone conjugate [Fe2Cp2(NH2OX)(CO)(mu-CO){mu-CN(Me)(2)}]CF3SO3, 3, was prepared from 1a, 3-(2-aminoethyl)-5-phenyloxazolidin-2-one (NH2OX) and Me3NO, and finally isolated in 96% yield. In contrast, the one pot reactions of 1a-b with NHEt2 in the presence of Me3NO gave the unstable [Fe2Cp2(NHEt2)(CO)(mu-CO){mu-CN(Me)(R)}]CF3SO3 (R = Me, 4a; R = Cy, 4b) as unclean products. All diiron complexes were characterized by analytical and spectroscopic techniques; moreover, the behavior of 2a-c and 3 in aqueous media was ascertained.