V-Cu-S异金属簇合物的研究——Ⅰ.[VS_4(CuPPh_3)_4Br]的合成和晶体结构

The Study on the V-Cu-S Heterometallic Cluster——Ⅰ. Synthesis and Crystal Structure of [VS_4(CuPPh_3)_4Br]

以(NH_4)_3VS_4为起始原料,用低温固相法合成了标题簇合物,并测定其晶体结构.晶体属空间群P(?),单胞参数a=1.3139(10),b=2.5113(17),c=1.1800(8)nm,α=93.04(6)β=114.86(5),γ=96.71(7),Z=2,μ=21.4cm^(-1),R=0.084.在簇合物中,VS_4^(3-)保持较严格的四面体构型,并螯合四个Cu(I)离子连同桥Br-离子形成具有额外面的立方烷簇骼[VS_4Cu_4Br].

The title compound was prepared by solid state reaction of the mixture with mole-ratio (NH4)3VS4: CuCl: PPh,: Et4NBr = 1: 2: 3: 1 at 100℃, 12 hours. The crystal structure was determined from single crystal X-ray diffraction data. It crystallizes in triclinic, space group P1, a = 1.3139(10), b = 2.5113(17), c = l. 1800(8 )nm, α= 93.04(6), β=114.86(5), γ=96.71(7)°, Z = 2, μ= 21.4cm-1, R = 0.084. In the title cluster, VS43- retain more serious tetrahedral configulation and chelates with four Cu(Ⅰ) ions together with bridged Br- formed a cubane with an extra face [VS4Cu4Br] core.