Hypercoordinated organotin compounds containing sulfur and chlorine. Molecular structures of [(Ph3P)(2)N](+)[S(SnR2Cl)(2)Cl](-) (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)(2)S (1, R = Me; 2, R =n- Bu; 3, R = t-Bu). H-1-, C-13-, and Sn-119-NMR studies indicate that these c ompounds are kinetically labile and in equilibrium with the starting materi als, Addition of equimolar amounts of [(Ph3P)(2)N]Cl to the reaction mixtur es gave the chloride complexes [(Ph3P)(2)N](+)[S(SnR2Cl)(2)Cl](-) (4, R = M e; 5, R = n-Bu; 6, R = t-Bu). Single-crystal X-ray diffraction studies reve aled the tin atoms in both 4 and 6 to adopt distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions. (C) 2 001 Elsevier Science B.V. All rights reserved.