Synthesis and reactivity of iron carbonyl clusters containing alkynethiolate ligands

The new cluster Li[Fe3(μ3,η1-SCtriple bond; length of mdashCFc)(CO)9] reacts with ClAuPPh3 to afford compound [Fe3Au(μ4,η2-Ctriple bond; length of mdashCFc)(CO)9(PPh3)], which exhibits an isomeric equilibrium in solution with the cluster [Fe3Au(μ3,η2-Ctriple bond; length of mdashCFc)(CO)9(PPh3)].The rupture of C–S bonds in the thioethers Me3SiCtriple bond; length of mdashCSCtriple bond; length of mdashCR (R = Fc, SiiPr3) in the presence of Fe3(CO)12, yields to the clusters [Fe3(μ-SCtriple bond; length of mdashCSiiPr3)(μ-Ctriple bond; length of mdashCSiMe3)(CO)9] and [Fe3(μ,η2-(SiiPr3)CCsingle bondCtriple bond; length of mdashCSiMe3)(μ3-S)(CO)9] together with the unexpected compounds [Fe2(μ-SCdouble bond; length as m-dashC(H)R)(CO)6] (R = SiMe3, SiiPr3).Additionally, the dinuclear derivatives [Fe2(μ-SCtriple bond; length of mdashCR)(μ-Ctriple bond; length of mdashCR′)(CO)6] (R = Fc, R′ = SiMe3; R = SiMe3, R′ = Fc; R = SiMe3; R′ = SiiPr3) have also been obtained. These compounds have been spectroscopically characterized and the crystal structure of some of them has been solved.