簇合物[Et4 N]8[Mo2 S4(SCH2 CH2 S)2]4的合成及其结构

在室温无水无氧充氮条件下,以(NH4)2MoS4,Et4NBr和HSCH2CH2SH为原料,合成[Et4N]8[Mo2S(SCH2CH2S)2]4簇合物,用X射线衍射法测得其晶胞参数为:a=2.604 4 nm,b=1.986 6 nm,c=2.630 2 nm,V=13.585 81 nm3,Z=4,晶体属单斜晶系.晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0.088 7.研究结果表明,[Mo2S4(SCH2CH2S)2]2-为含Mo-Mo金属健的双核阴离子;每个Mo原子被5个硫原子配位,构成近四棱锥配位的几何构型,2个四棱锥共1条底边,每个四棱锥的1个顶点被1个端基硫原子占有,形成环笼状结构.[Et4N]8[Mo2S4(SCH2CH2S)2]4簇合物红外光谱的主要特征波出现在渡数为510,460,430和340 cm-1处;紫外可见光谱在波长为305,380和435 nm处有吸收峰出现.

Synthesis and structure of cluster [Et4N]8[Mo2S4(SCH2CH2S)2]4

A novel cluster was prepared by using (NH_4)_2MoS_4, Et_4NBr, HSCH_2CH_2SH as the reaction materials at room temperature under pure nitrogen gas and atmosphere of free oxygen and water. The structure of the cluster was determined by X-ray method. The parameters of the crystal cell of the cluster are as follows: a =2.604 4 nm, b =1.986 6 nm, c =2.630 2 nm, V =(13.585 81) nm~3 and Z =4, the space group is P(21)/n. After the structure was refined by block-(diagonal) matrix least square method, and the final agreement factor is R =0.088 7. The results show that the binuclear anion contains two molybdenum atoms. Each molybdenum atom is ligated by five sulfur atoms to form approximately tetragonal pyramid (TP) coordination geometry and two TP sharing a basal edge forms a cage structure. The infrared spectra indicate there are characteristic waves at 510, 460, 430 and 340 cm~(-1),respectively, and the ultraviolet-visible spectra indicate there are absorption peaks at 305,380 and 435 nm, respectively.