Abstract:
The title compounds 1,3-propanediammonium tetrathiomolybdate, (1,3-pnH(2))[MoS4], 1 and, NNN',N'-tetramethylethylenediammonium tetrathiomolybdate, (tmenH(2))[MoS4], 2, were prepared by reacting the ammonium salt of [MoS4](2-) with the corresponding organic diamine.In I and 2 the organic diamines 1,3-propanediamine (1,3-pn) and NNN',N-tetramethylethylenediamine (tmen) are present in their diprotonated form. The reaction of 1 or 2 with [Ni(en)(3)]Cl-2.2H(2)O (en is ethylenediamine) results in the formation of the highly insoluble complex tris(ethylenediamine)Ni(II) tetrathiomolybdate, [Ni(en)(3)][MoS4], in quantitative yields. 1 and 2 have been characterized by chemical analysis, vibrational, UV-Vis and NMR spectroscopy, TG-DTA-MS and single crystal X-ray crystallography. Compound 1 is thermally more stable compared to 2. Both complexes decompose in a single step forming amorphous molybdenum sulfide. The structure of the title complexes can be described as consisting of tetrahedral [MoS4](2-) dianions which accept a complex series of H-bonds from the organic dications. The strength and number of these hydrogen bonds affect the Mo-S bond lengths.
