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)Å, 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)Å, 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)Å, β= 106.32(4)°, R= 0.055.