Ternary Nanoclusters of CuHgS, CuHgSe, and CuInS

Two copper−mercury−chalcogenide clusters [Hg15Cu20E25(PPr3)18] (1, E = S; 2, E = Se) are synthesized in good yield from the reaction of (Pr3P)3Cu−ESiMe3 and (Pr3P)2·Hg(OAc)2 at low temperatures. Single-crystal X-ray analyses illustrate that the two ternary clusters are isomorphous and consist of a phosphine-stabilized core of mixed Hg, Cu, and E centers. Thermolysis of 1 leads to the formation of mercury metal and various forms of copper−sulfide. The copper−indium−sulfide cluster [Cu6In8S13Cl4(PEt3)12] (3) is similarly prepared in 50% yield from (Et3P)3Cu−SSiMe3, InCl3, and S(SiMe3)2.