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  

The Synthesis Structural Characterization and Reactivity of a Mo-Ag Cubane-Like Heterometallic Tetranuclear Cluster [Mo_2Ag_2S_4](TDT)_2(PPh_3)_2

作　　者：陈红兵[1] 卢绍芳[1] 黄建全[1] 吴锵金[1] 黄小荥[1] 

机构地区：[1]中国科学院福建物质结构研究所

出　　处：《化学学报》1994年第11期1088-1094,共7页Acta Chimica Sinica

摘　　要：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)_2CH_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.Taking [Mo2S4(TDT)2] (Me4N)2 (1, TDT = S2C6H3CH32- ) 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 first example for the compound containing [Mo2Ag2S4]4+ cluster core. In this paper, the results of IR, UV-Vis, a single crystal X-ray study and electrochemical CV curve for the compounds 2 are reported. When this cluster react with a excess Cu(PPh3)2dtp, its copper analogy [Mo2Cu2S4](TDT)2(PPh3)2 was isolated. This reaction can be regarded as a metal replacement reaction, which is a novel type of reaction so far.Crystal data of 2: Monoclinic, S.G. P21 / n. a= 1.7202(4)nm, b= 1.7632(3)nm, c= 1.9033(8) nm, β=99.24(3)°, V= 5.698(3)nm3, Z=4, Dc= 1.69g/cm3 For 6158 reflections. ?0.040, Rw = 0.048.

关 键 词：钼-银 四核原子簇 晶体结构 设计合成 

分 类 号：O641.4[理学—物理化学]