The preparation and characterization of polysulfanotungsten complexes of the type (η5-C5H5)W(CO)3SxR, where x = 2, 3 and (η5-C5H5)W(CO)3SS(O)R, where R = CH2C6H5, p-C6H4CH3

Abstract

The polysulfano complexes (η5-C5H5)W(CO)3Q, where Q = SSR, SSSR, SS(O)R, and R = CH2C6H5 and p-C6H4CH3 have been prepared via treatment of (η5-C5H5)W(CO)3SH with RSphth, RSSphth, and RS(O)phth, respectively, at −20 °C, where phth = N-phthalimido. The complexes where Q = SSR and SSSR lost sulfur spontaneously in solution to give the thiolato complexes (η5-C5H5)W(CO)3SR and the disulfano complexes, respectively. The presence of PPh3 accelerated this reaction for Q = SSR. Treatment of (η5-C5H5)W(CO)3SSR with m-chloroperbenzoic acid gave a mixture of complexes for which Q = SR, SO2R, SS(O)R, and higher oxidized sulfur ligands. As(C6H5)4[W(CO)5SH] reacted with p-CH3C6H4Sphth to give an unstable first product, tentatively identified as As(C6H5)4[W(CO)5SS-p-C6H4CH3], the isolated product being As(C6H5)4[W(CO)5S-p-C6H4CH3].