Exploration of metal sulfide syntheses and the dissolution process of antimony sulfide in phosphonium-based ionic...

Ionic liquids (ILs), especially task-specific ILs, are capable of dissolving various solids at moderate temperatures without the need for special reaction vessels. Direct synthesis of binary sulfides of B, Bi, Ge, Mo, Cu, Au, Sn, In, Ti, V, Fe, Co, Ga, Ni, Al, Zn, and Sb in [P₆₆₆₁₄]Cl was tested at 100 °C, i.e. below the melting point of sulfur. Under these conditions, substantial sulfide formation occurred only for nickel (Ni₃S₄, Ni₃S₂, NiS) and copper (Cu₂S, CuS). Sb showed no formation of crystalline sulfide, but after addition of EtOH, an orange material precipitated which was identified as amorphous metastibnite. Subsequently, the dissolution of antimony sulfide (Sb₂S₃), the main source of antimony production, in the phosphonium-based ILs [P₆₆₆₁₄][OAc] and [P₆₆₆₁₄]Cl at 100 °C was studied in detail. The dissolution proceeds without H₂S evolution, and amorphous Sb₂S₃ can be precipitated from these solutions. Heating Sb₂S₃ in the Lewis-acidic IL [BMIm]Cl·4.7AlCl₃ led to the crystallization of [Sb₁₃S₁₆Cl₂][AlCl₄]₅, which contains a new quadruple heterocubane cation.