Use of (NSCl) 3 as a Chain-Building Reagent,I: Reaction of ArS 3 N 2 Ar with (NSCl) 3 in the Presence of AgAsF 6 to Form the Chain-Lengthened Product,[ArS 4 N 3 Ar] [AsF 6 ]

Abstract

Reaction of ArS₃N₂Ar [Ar = Ph, p-O₂N.C₆H_4⁻ ], 1, with (NSCl)₃ led to the formation of the chain-lengthened products [ArS₄N₃Ar] C1, which were converted to the corresponding hexafluorarsenate (V) salts [ArS₄N₃Ar][AsF₆], 2, by metathesis with AgAsF₆. The crystal structure of the para-nitrophenyl derivative, 2a, is reported and is monoclinic, space group P2₁/c; a = 6.1490(12), b = 17.723(4), c = 18.967(4)Å, β = 87.99(3)° with D_c= 1.94 gcm⁻³, Z = 4 and R1 (2899 unique data) = 0.11. When Ar = o-O₂N·C₆H_4⁻, the chain-lengthened product could only be achieved in the presence of both (NSCl)₃ and AgAsF₆. A mechanism is postulated.