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Potassium N-R-sulfonyldithiocarbimates, K2(RSO2N=CS2) (R = Me, Ph, 2-MeC6H4), react with Pd(OAc)2 to yield complex anions bis(N-R-sulfonyldithiocarbimato)palladate(II), [Pd(RSO2N=CS2)2]2−, which were isolated as their n-Bu4N+ salts. When the reaction was performed in the presence of Ph3P in a 2:1 ratio with respect to Pd(OAc)2, the N-R-sulfonyldithiocarbimatobis(triphenylphosphine)palladium(II) complexes were obtained. Elemental analyses, i.r. spectra and electronic spectra data were consistent with the formation of palladium–sulfur diamagnetic square planar complexes in the first case and mixed square planar complexes of palladium with Ph3P and dithiocarbimates in the second case. The 1H-n.m.r., 13C-n.m.r. and 31P-n.m.r. spectra showed the expected signals for the Bu4N+ cation, Ph3P and the dithiocarbimate moieties.