Preparation, crystal structure and spectroscopic characterization of novel N-R-sulfonyldithiocarbimate platinum(II) complexes

Potassium N-R-sulfonyldithiocarbimates, K-2(RSO2N=CS2), react with K-2[PtCl4] in water/methanol to yield complex anions bis(N-R-sulfonylditliiocarbimato)platinate(II), [Pt(RSO2N=CS2)(2)](2-) (R = C6H5 (1) and 4-BrC6H4 (2)) which were isolated as their n-(BuN+)-N-4 safts.The single crystal X-ray analysis showed that (Bu4N)(2)[Pt(C6H5SO2N=CS2)(2)] crystallizes in the triclinic space group P1, and (Bu4N)(2)[Pt(4-BrC6H4SO2N=CS2)(2)] crystallizes in the monoclinic space group P2(1)/c with disorder in the two chains of the two univalent Bu4N+ cation and 4-BrC6H4 groups of the anion. All complexes present a similarly distorted square-planar configuration due to the asymmetric bidentate chelation by two sulfur atoms. In both compounds the Pt atoms are in the crystallographic center of symmetry. Elemental analyses, IR spectra and electronic spectra were also consistent with the formation of platinum-sulfur diamagnetic square planar complexes. The H-1 NMR, C-13 NMR and Pt-195 NMR spectra showed the expected signals for the n-Bu4N+ cation and the anionic complexes. (C) 2004 Elsevier Ltd. All rights reserved.