REACTION OF [SNS][ASF6] WITH HG(CN)(2) AND PHHGCN - PREPARATION AND CRYSTAL-STRUCTURES OF [HG(CNSNS)(2)][ASF6](2) AND [PHS(4)N(3)PH][ASF6]

Reaction of HS(CN)(2) with two equivalents of the salt [SNS][AsF6] pro vided a high yield (92%) route to the first metallo-dithiadiazolylium salt, [Hg(CNSNS)(2)][AsF6](2) (I). Its structure and reactivity are co mpared with those of the analogous organic derivatives, [R.CNSNS][AsF6 ]; I initiates the polymerization of tetrahydrofuran and undergoes met athesis reactions but reduction leads to decomposition (forming S4N4), whilst oxidation with the halogens provides a novel route to the salt s [X.CNSNS][AsF6] (X = Cl, Br and I). In contrast, reaction of PhHgCN with [SNS][AsF6] yielded the sulfur-nitrogen chain compound, [PhS(4)N( 3)Ph][AsF6] (II) with a cation consisting of an alternating S/N chain strung between two phenyl groups.