Synthesis and reactivity of iron carbonyl clusters containing alkynethiolate ligands

The new cluster LiFe₃(μ₃,η¹-SCCFc)(CO)₉] reacts with ClAuPPh₃ to afford compound Fe₃Au(μ₄,η²-CCFc)(CO)₉(PPh₃)], which exhibits an isomeric equilibrium in solution with the cluster Fe₃Au(μ₃,η²-CCFc)(CO)₉(PPh₃)].The rupture of C-S bonds in the thioethers Me₃SiCCSCCR (R = Fc, SiⁱPr₃) in the presence of Fe₃(CO)₁₂, yields to the clusters Fe₃(μ-SCCSiⁱPr₃)(μ-CCSiMe₃)(CO)₉] and Fe₃(μ,η²-(SiⁱPr₃)CCCCSiMe₃)(μ₃-S)(CO)₉] together with the unexpected compounds Fe₂(μ-SCC(H)R)(CO)₆] (R = SiMe₃, SiⁱPr₃).Additionally, the dinuclear derivatives Fe₂(μ-SCCR)(μ-CCR′)(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.