镉与二乙基二硫代氨基甲酸配合物的合成、结构与热分解动力学

Synthesis,Struture and Thermal Decomposition Kinetics of the Complexes of Cadmium with Diethyldithiocarbamate

采用常温固相法合成了镉与二乙基二硫代氨基甲酸根的配合物（Cd2L4）,以二氯甲烷为溶剂培养得到了单晶体,并测定了它们的晶体结构.配合物Cd2L4晶体属于单斜晶系,空间群P21/n,晶胞参数a=10.0315,b=10.7850,β=103.9100°,c=16.0234,R1=0.0211,wR2=0.0475,每个Cd（Ⅱ）原子的配位数都为5,配位构型为变形的四方锥,锥底的配位原子为两个配体的四个硫原子,锥顶的配位硫原子为另一四方锥锥底的一个硫原子,该硫原子将两个四方锥互相连接在一起,Cd（Ⅱ）原子间的距离为3.598;配合物在251℃熔化并在271～341℃分解,通过Coats-Redfern和MKN法对数据进行拟合得分解的积分动力学模式函数G（α）=α,活化能E=182.4kJ·mol-1,指前因子lgA=13.7704,动力学补偿效应方程为lgA=0.08755E-2.353。

The complexes with the formula of Cd2L4（where L is diethyldithiocarbamate）are synthesized by solid state reaction at room temperature.The single crystal crystalized from its solution in dichloromethane is analyzed by x-ray single crystal analysis.The crystal structure of Cd2L4 belongs to monoclinic space group P21/n with a=10.0315（10）,b=10.7850（10）,β=103.9100（10）°,c=16.0234（15）,R1=0.0211,wR2=0.0475.Each cadmium has five-coordinated sulfur atoms with distorted pyramid environment.The four bottom sulfur atoms come from two ligands,the top sulfur atom is one of the other pyramid＇s bottom sulfur atoms,and it acts as bridged atom to join the two pyramids together.The distance of two cadium atom in molecule is 3.598.The complex melt at 251℃ and then decomposed in the range of 271～341℃.The data from nonisothermal experiment is analyzed by Coats-Redfern and MKN method.The result shows that the integral kinetic function is G（α）=α,activation energy is E=182.4kJ·mol-1,preexponential factor lgA=13.7704,and the kinetic compensation effect equation is lgA=0.08755E-2.353.