THE PREPARATION AND CHARACTERIZATION OF POLYSULFANOTUNGSTEN COMPLEXES OF THE TYPE (ETA-5-C5H5)W(CO)3SXR, WHERE X = 2,3 AND (ETA5-C5H5)W(CO)3SS(O)R, WHERE R = CH2C6H5, P-C6H4CH3

The polysulfano complexes (i-C5H5)W(CO)3Q where Q = SSR SSSR SS(O)R and R = CH2C6H5 and p-C6H4CH3 have been prepared via treatment of (5-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 (5-C5H5)W(CO)3SR and the disulfano complexes respectively. The presence of PPh3 accelerated this reaction for Q SSR. Treatment of (q5-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].