Grasser Matthias A, Pietsch Tobias, Brunner Eike, Ruck Michael
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany.
Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, 01187 Dresden, Germany.
Dalton Trans. 2022 Mar 8;51(10):4079-4086. doi: 10.1039/d1dt04165g.
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 [P]Cl was tested at 100 °C, below the melting point of sulfur. Under these conditions, substantial sulfide formation occurred only for nickel (NiS, NiS, NiS) and copper (CuS, 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 (SbS), the main source of antimony production, in the phosphonium-based ILs [P][OAc] and [P]Cl at 100 °C was studied in detail. The dissolution proceeds without HS evolution, and amorphous SbS can be precipitated from these solutions. Heating SbS in the Lewis-acidic IL [BMIm]Cl·4.7AlCl led to the crystallization of [SbSCl][AlCl], which contains a new quadruple heterocubane cation.
离子液体（ILs），尤其是特定任务型离子液体，能够在适中温度下溶解各种固体，无需特殊反应容器。在低于硫熔点的100℃下，测试了在[P]Cl中直接合成硼、铋、锗、钼、铜、金、锡、铟、钛、钒、铁、钴、镓、镍、铝、锌和锑的二元硫化物。在这些条件下，仅镍（NiS、NiS、NiS）和铜（CuS、CuS）有大量硫化物生成。锑未形成结晶硫化物，但加入乙醇后，有橙色物质沉淀，鉴定为非晶态偏锑矿。随后，详细研究了锑生产的主要来源硫化锑（SbS）在100℃下于鏻基离子液体[P][OAc]和[P]Cl中的溶解情况。溶解过程中无硫化氢逸出，且可从这些溶液中沉淀出非晶态SbS。在路易斯酸性离子液体[BMIm]Cl·4.7AlCl中加热SbS会导致[SbSCl][AlCl]结晶，其含有一种新的四重杂立方烷阳离子。
