A GENERAL-ROUTE TO N(SCL)2+ AND SNS+ SALTS

A 1:3 mixture of (NSCl)3 and AgX (where X is a 'hard' anion) in liquid SO2 act as a convenient source of [SN]X. The reactivity of salts of this SN+ cation towards sulfur and SCl2 has been examined. Reaction of (NSCl)3 with AgX (X = AsF6, SbF6 or CF3SO3) and SCl2 in liquid SO2 gave [N(SCl)2]X in high yield (> 75%). Reduction of these salts with SnCl2 provides a convenient route to the corresponding [SNS]X salts. Replacement of SCl2 by sulfur in the (NSCl)3 + AgCF3SO3 reaction yields only ca. 30% [SNS][CF3SO3]. The other main product is [S6N4][CF3SO3]2 which crystallises in the space group P2(1)/n [Z = 2, a = 8.632(4), b = 10.614(8), c = 8.387(6) angstrom, beta = 90.79(5)-degrees, R = 0.025] and shows similar intermolecular S ... O contacts to [S6N4][ClS2O6]2 [P1BAR, Z = 1, a = 7.689(1), b = 10.726(1), c = 6.614(1) angstrom, alpha = 101.00(2), beta = 114.42(2), gamma = 90.35(2)-degrees, R = 0.031]. The relative reactivities of the different SNS+ salts with PhCN lie in the order AsF6- > SbCl6- > CF3SO3- > SbF6- > AlCl4-. The structure of [PhCNSNS][AsF]6 has been determined: space group P2(1)/a, Z = 4, a = 10.824(5), b = 8.287(2), c = 13.599(3) angstrom, beta = 106.32(4)-degrees, R = 0.055.