Affiliations: Department of Chemistry, The University of Durham, South Road, Durham DH1 3LE. U.K.
Note:  Corresponding author.
Abstract: Reaction of ArS3N2Ar [Ar = Ph, p-O2N.C6H4− ], 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 Dc= 1.94 gcm−3, Z = 4 and R1 (2899 unique data) = 0.11. When Ar = o-O2N·C6H4−, the chain-lengthened product could only be achieved in the presence of both (NSCl)3 and AgAsF6. A mechanism is postulated.