Reaction of [SNS][AsF 6] with Hg(CN) 2 and PhHgCN: Preparation and crystal structures of [Hg( ) 2][AsF 6] 2 and [PhS 4N 3Ph][AsF 6]

Reaction of Hg(CN) 2 with two equivalents of the salt [SNS][AsF 6] provided a high yield (92%) route to the first metallo-dithiadiazolylium salt, [Hg( ▪) 2][AsF 6] 2( I). Its structure and reactivity are compared with those of the analogous organic derivatives, [R. ▪][AsF 6]; I initiates the polymer...

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Bibliographic Details
Published in:Polyhedron 1996, Vol.15 (11), p.1877-1886
Main Authors: Aherne, Christine M., Banister, Arthur J., Lavender, Ian, Lawrence, Simon E., Rawson, Jeremy M., Clegg, William
Format: Article
Language:English
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Summary:Reaction of Hg(CN) 2 with two equivalents of the salt [SNS][AsF 6] provided a high yield (92%) route to the first metallo-dithiadiazolylium salt, [Hg( ▪) 2][AsF 6] 2( I). Its structure and reactivity are compared with those of the analogous organic derivatives, [R. ▪][AsF 6]; I initiates the polymerization of tetrahydrofuran and undergoes metathesis reactions but reduction leads to decomposition (forming S 4N 4), whilst oxidation with the halogens provides a novel route to the salts [X. ▪][AsF 6] (X = Cl, Br and I). In contrast, reaction of PhHgCN with [SNS][AsF 6] yielded the sulfur-nitrogen chain compound, [PhS 4N 3Ph][AsF 6] ( II) with a cation consisting of an alternating S/N chain strung between two phenyl groups.
ISSN:0277-5387
DOI:10.1016/0277-5387(95)00426-2