Abstract
Pure sodium tetrasulfide (Na2S4) was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at 25 °C and at concentrations below 10 micromolar of S42–. A series of S42– complexes of these metals were found to exist by voltammetric methods. At higher concentrations, S42– reacted to give MS and S8. Tetrasulfide complexes with compositions assigned as [M(η1‐S4)] and [M2(μ‐S4)]2+ or [M2 Zn>Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(η1‐S4)]. Both Cu and Zn displace Mn, Fe, Co and Ni from their tetrasulfide complexes. The differences in metal tetrasulfide chemistry can be explained by a consideration of molecular orbital stabilization energies.
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