Donor Solvent Mediated Reactions of Elemental Zinc and Sulfur, sans Explosion

Atul K. Verma, Thomas B. Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review


The reactions of zinc powder with solutions of elemental sulfur in various donor solvents is described. Complexes of the type ZnS6(N-donor)2 are obtained for the ligands tetramethylethylenediamine (TMEDA), N-methylimidazole (MeIm), and 4-(N,N-dimemylamino)pyridine (DMAP). Ligand competition studies on pyridine solutions revealed that the relative stability constants (DMAP > MeIm > TMEDA > pyridine) parallel the basicity of the ligands. The TMEDA complex crystallizes in the monoclinic space group C2/c with a = 12.255(3) Å, b = 10.559(2) Å, c = 12.392(2) Å, and β = 110.22(2)°. In the solid state ZnS6(TMEDA) adopts a tetrahedral geometry with a seven-membered ZnS6 ring. A variety of reactivity studies were conducted on ZnS6(TMEDA). Solutions of ZnS6(TMEDA) undergo ligand exchange with quinuclidine and MeIm to afford ZnS6L2 (L = MeIm, quinuclidine). The anionic species [ZnS12]2- is formed upon addition of (PPh4)2S6 to ZnS6(TMEDA). Optical and reactivity studies showed that MeIm, but not pyridine, displaces the polysulfide from ZnS6(MeIm)2 as indicated by the appearance of the chromophore S3-. ZnS6(TMEDA) reacts with the electrophilic acetylenes dimethyl acetylenedicarboxylate and methyl propiolate to give the dithiolene complexes ZnS2C2R(CO2Me)(TMEDA) {R = CO2Me, H}. Solid ZnS6(TMEDA) cleanly decomposes at 350 °C as indicated by TGA studies. Preparative scale conversions at 500 °C affords cubic ZnS. Submicron cubic ZnS is generated upon partial desulfurization of ZnS6(TMEDA) with tertiary phosphines as established by electron microscopic studies.

Original languageEnglish (US)
Pages (from-to)3072-3078
Number of pages7
JournalInorganic Chemistry
Issue number11
StatePublished - May 1 1995

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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