AlCl_3催化1,1,1-三甲基-2,2,2-三氯二硅烷裂解的理论研究

Theoretical Study of the Cracking Reaction of 1,1,1-trimethyl-2,2,2-trichloro-disilane with Aluminium Trichloride as Catalyst

结合采用DFT(B3LYP)及二级微扰方法对AlCl3催化1,1,1-三甲基-2,2,2-三氯二硅烷裂解反应的机理进行了研究.通过计算数据结果表明,此裂解反应为放热反应,理论产率比较高.反应可以同时按2种通道进行,其中通道2反应较为容易,其3步反应的焓变依次为:ΔH1(86.963 kJ.mol-1),ΔH2(-237.596 kJ.mol-1),ΔH3(-127.568 kJ.mol-1).通道2的各步正反应活化能数值表明,第3步为速控步,其正反应的活化能E3为214.913 kJ.mol-1.

The mechanism of the cracking reaction of 1,1,1-tetramethyl-2,2,2-trichloro-disilane dichloride with aluminium trichloride as catalyst was investigated by DFT and perturbation methods.The data results of calculation showed that the reaction of 1,1,1-trimethyl-2,2,2-trichloro-disilane was exothermic,and the theoretical-yield was higher.The reaction could be proceeded in two channels,the second channel was easier.The reaction could be divided into three steps,the enthalpy of each step were： ΔH1（86.963 kJ·mol-1）,ΔH2（-237.596 kJ·mol-1）,ΔH3（-127.568 kJ·mol-1）,respectively.The activation energy of each step in the second channel showed that the third step reaction was the rate determining step,and the activation energy E3 of the forward reaction was 214.913 kJ·mol-1.