A general route to N(SCl)2 + and SNS+ salts

Abstract

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 P21/n[Z= 2, a= 8.632(4), b= 10.614(8), c= 8.387(6)A, β= 90.79(5)°, R= 0.025] and shows similar intermolecular S ⋯ O contacts to [S6N4][ClS2O6]2[P, Z= 1, a= 7.689(1), b= 10.726(1), c= 6.614(1)A, α= 101.00(2), β= 114.42(2), γ= 90.35(2)°, 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 [Ph[graphic omitted]][AsF]6 has been determined: space group P21/a, Z= 4, a= 10.824(5), b= 8.287(2), c= 13.599(3)A, β= 106.32(4)°, R= 0.055.