Hypercoordinated organotin compounds containing sulfur and chlorine. Molecular structures of [(Ph3P)2N]+[S(SnR2Cl)2Cl]− (R=Me, t-Bu)

The reaction of diorganotin sulfides, cyclo-(R2SnS)n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin dichlorides, R2SnCl2, provided the tetraorganodistannathianes, (R2ClSn)2S (1, R=Me; 2, R=n-Bu; 3, R=t-Bu). 1H-, 13C-, and 119Sn-NMR studies indicate that these compounds are kinetically labile and in equilibrium with the starting materials. Addition of equimolar amounts of [(Ph3P)2N]Cl to the reaction mixtures gave the chloride complexes [(Ph3P)2N]+[S(SnR2Cl)2Cl]− (4, R=Me; 5, R=n-Bu; 6, R=t-Bu). Single-crystal X-ray diffraction studies revealed the tin atoms in both 4 and 6 to adopt distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions.