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Sulfur transfer reactions of a zinc tetrasulfanido complex.

A zinc tetrasulfanido complex supported by a bis(carboxamide)pyridine ligand framework has been synthesized by the insertion of elemental sulfur into the zinc-S(thiolate) bond of a zinc dithiolate complex ([LZn]2-). This paper reports on sulfur transfer reactions of this polysulfanido complex ([1]2-) and compares this behavior to known reactions of metal polysulfido complexes. Complex [1]2- was demonstrated to be in exchange with [LZn]2- and free elemental sulfur in solution. Although triphenylphosphine abstracts sulfur from [1]2- to form [LZn]2-, complex [LZn]2- can abstract sulfur from the zinc polysulfido complex (TMEDA)ZnS6 (TMEDA = N,N,N',N'-tetramethylethylenediamine). The tetrasulfanido complex [1]2- can also transfer sulfur to dimethyl acetylenedicarboxylate to form a zinc dithiolene complex. These studies demonstrate that the zinc complex with a tetrasulfanido moiety can undergo similar reactions as metal complexes with purely inorganic polysulfido groups, although the final metal-containing products are different.