Activation of C-S bonds in organosulfur compounds containing alpha,beta-unsaturated ketone systems by carbonylruthenium and -iron complexes

Abstract

Vinylidenetetraruthenium clusters have been obtained from the reactions between [Ru-3(CO)(12)] and [CH3C(O)CH=C(SCH3)(2)] or [(C5H5)Fe{C5H4CH=CHC(O)CH=C(SCH2CH2S)}] by cleavage of the S-C sp(2) bonds in these ligands. An excess of [CH3C(O)CH=C(SCH3)(2)] afforded the dinuclear complex [Ru-2(CO)(4)(mu-SCH3)(2){eta(2):kappa-C,O-C(SCH3)CHC(O)CH3}(2)], which was then converted into the vinylidene cluster [Ru-4(CO)(10)(mu-SCH3)(2){mu(4),eta(3):kappa-C,C,O-C=CHC(O)CH3}] in the presence of more of the carbonylruthenium complex. However, the carbonyliron complex led to the formation of the dinuclear compounds [Fe-2(CO)(4) (mu-SCH3)(2){eta(2):kappa-C,O-C(SCH3)CHC(O)CH3}(2)] and [Fe-2(CO)(5){mu,eta(4):kappa-C,O,S,S- (SCH2CH2S)C=CHC(O)CH=CHC5H4}Fe(C5H5)]. All of the new complexes exhibit a pentametallacycle group as a consequence of the rupture of the S-C bonds, as well as the presence of the C(O)R substituent in these ligands. The compounds have been characterised by analytical and spectroscopic data and the crystal structures of some of them have been solved by X-ray diffraction.