NEW SYNTHESIS OF [SFE3(CO)(9)](2-) AND ITS REACTIVITY TOWARD ELECTROPHILES

The reaction of Na2SO3 with Fe(CO)(5)/KOH in methanol forms the tetrah edral cluster [SFe3(CO)(9)](2-) in good yield. Acidification of [SFe3( CO)(9)](2-) with H+ forms the monohydrido; cluster [SFe3(mu-H)(CO)(9)] (-) (I) and the dihydrido cluster SFe3(mu-H)(2)(CO)(9). Further methyl ation of [SFe3(CO)(9)](2-) with MeSO3CF3 produces the sulfur-methylate d cluster [MeSFe3(CO)(9)](-) (II), When [SFe3(CO)(9)](2-) is treated w ith Ru-3(CO)(12) in refluxing acetone, the octahedral cluster [SFe2Ru3 (CO)(14)](2-) (III) is obtained. Subsequent methylation of III with Me SO3CF3 gives the octahedral cluster [MeSFe2Ru3(CO)(14)](-)(TV), in whi ch the sulfur atom is pentacoordinated to one methyl group and two Ru and two Fe atoms. Clusters I-IV have been fully structurally character ized by spectroscopic methods and X-ray analysis. In this paper, the b asic sites of [SFe3(CO)(9)](2-) are studied in terms of the differing electrophiles, and a novel pentacoordinate bonding mode of the sulfur atom is also found in cluster N.