Mo-Ag类立方烷异四核簇[Mo~2Ag~2S~4](TDT)~2(PPh~3)~2的合成, 结构表征和反应性

采用[2+1+1]的设计合成模式, 以二核化合物[Mo~2S~4(TDT)~2](Me~4N)~2(1,TDT=S~2C~6H~3CH~3^2^-)为起始物,与Ag(PPh~3)~3(NO~3)反应,首次合成[Mo~2Ag~2S~4](TDT)~2(PPh~3)~2·CH~2Cl~2(2)的类立方烷异四核簇合物.文中报道了该化合物的晶体结构,红外光谱,紫外可见光谱和电化学研究结果, 以此簇合物和过量的Cu(PPh~3)~2dtp[dtp=S~2P(OEt)~2]反应发现金属Ag可被Cu取代,形成其同系物[Mo~2Cu~2S~4](TDT)~2(PPh~3)~2.这是迄今研究较少的原子簇反应类型.化合物的结晶学参数如下:单斜晶系,空间群:P2~1/n,晶胞参数:a=1.7202(4)nm,b=1.7632(3)nm,c=1.9033(8)nm.β=99.24(3)°,V=5.698(3)nm^3,Z=4,D~c=1.69g/cm^3.对于6158个衍射,最终结构偏离因子R=0.040,R~W=0.048

The synthesis structural characterization and reactivity of a Mo-Ag cubane-like heterometallic tetranuclear cluster [Mo~2Ag~2S~4](TDT)~2 (PPh~3)~2

Taking (Me4N)2[Mo2S4(TDT)2] (1, TDT = 4-methyl-1,2-benzenedithiolate) as starting material, [Mo2Ag2S4](TDT)2(PPh3)2 (2) was obtained from the reaction of 1 with Ag(PPh3)3(NO3) by [2+1+1] mode. This is the 1st example for the compound containing [Mo2Ag2S4]4+ cluster core. The results of IR, UV-visible, a single crystal x-ray study and electrochem. CV curve for 2 are reported. When this cluster reacts with excess Cu(PPh3)2dtp (dtpH = HS2P(OEt)2), its Cu analog [Mo2Cu2S4](TDT)2(PPh3)2 was isolated. This reaction can be regarded as a metal replacement reaction, which is a novel type of reaction. Crystal data of 2: monoclinic, space group P21/n, a 1.7202(4), b 1.7632(3), c 1.9033(8) nm, b 99.24(3)? Z = 4, dc = 1.69 g/cm3 for 6158 reflections, R = 0.040, Rw = 0.048.