η~6—芳烃希土有机配合物的合成、结构及性能研究——Ⅰ.Sm(η~6—C_6H_6)(AlCl_4)_3的合成及晶体结构

STUDY ON THE SYNTHESIS, STRUCTURE AND CHEMISTRY OF η~6-ARENE ORGANOLANTHANOID COMPOUNDS Ⅰ. SYNTHESIS AND X-RAY STRUCTURE OF

经过铝粉加热活化的AlCl_3与SmCl_3在苯中反应,得到了Sm(η~6—C_6H_6)(AlCl_4)_3·C_6H_6单晶.其晶体属于三斜晶系,P1空间群,晶胞参数a=9.456(2)(?),b=9.765(3)(?),c=16.776(4)(?),α=96.00(2)°,β=93.76(2)°,γ=111.66(2)°,V=1422.55(?)~3,Z=2.晶体结构是采用Patterson和Fourier合成法解出的,所有非氢原子的坐标及各向异性热振动参数经块矩阵最小二乘法修正,最后偏离因子R=0.031,R_ω=0.035.分子结构中,中心离子Sm(Ⅲ)与六个Cl原子及一个苯环上的六个C原子成键.Sm-C键平均距离2.92(?),Sm-Cl平均距离2.83(?).与希土相连的六个Cl原子,其中之五构成平面五边形,整个分子呈大致的五角双锥形.

A new organolanthanoid compound with η6-arene ligand, Sm(η6-C6H6)(AlCl4)3 · C6H6 has been prepared by the reaction of activated A1C13, aluminum powder and SmCl3 in benzene and its structure has been established by X-ray crystallography. Crystal data: triclinic, space group Pl, a = 9.456(2)A, b = 9.765(3)A, c=16.776(4)A, α = 96.00(2)A, β=93.76(2), γ=111.66(2), V=1422.55A3, Z = 2. The structure was solved by Rant method and block martrix least-square techniques followed by Fourier synthesis for 5008 reflections with I> 3δ(I), R = 0.031, Rω=0.053. The central metal atom Sm(Ⅲ) bonds to six chlorine atoms and six carbon atoms in the benzene ring. The average Sm-C distance and Sm-Cl distance arc 2.92A and 2.83A, respectively. The coordination polyhedron is a distorted pentagonal bipyrimid with a chlorine atom on an apical position and the benzene ring on the other apical position.