Three new metal thiophosphate anions, [CoS4(Co(P3S8)2)2]4–, [Cr(P3S9)2]3–, and [Mn(P2S8)2]2– have been isolated as single crystals of EMIM (1-ethyl-3-methylimidazolium) salts from ionothermal reaction of the elements in [EMIM][CF3SO3] for the former two and [EMIM][BF4] for the later. The former compound is structurally unique from known thiophosphate anions, contains three cobalt atoms in two different coordination environments and oxidation states, and has bridging, polydentate P3S83– groups that coordinate to the cobalt atoms through both S and P atoms. The both the chromium and manganese thiophosphate anions contain octahedrally-coordinated metal atoms and are structurally similar to the known ions [Ni(P3S9)2]4– and [Ni(P2S8)2]2– respectively . The synthesis of these new compounds reinforces the viability of producing other novel thiophosphate through ionothermal synthesis, as well as the viability of using ionic liquids other than [EMIM][BF4]. Exploratory synthesis will be expanded to include other transition metals as well as new ionic liquids such as [BMIM][BF4] (BMIM= 1-butyl-3-methylimidazolium).

Ionothermal synthesis and characterization of [EMIM]4[CoS4(Co(P3S8)2)2], [EMIM]3[Cr(P3S9)2], and [EMIM]2[Mn(P2S8)2]

251st National Meeting (2016)

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