二硅烯化合物顺反异构化过渡态动力学参数的计算

本文介绍了过渡态理论对双键取代物顺反异构化过程的处理方法. 计算了1,2-二叔丁基-1,2-二(2,4,6-三甲苯基)二硅烯、1,2-二[二(三甲硅基)]-氨基-1,2-二(2,4,6-三甲苯基)二硅烯和1,2-二甲基-1,2-二苯基二硅烯等化合物的顺反异构化的活化熵变和相应过程的Arrhenius A因子. 前两个化合物的计算结果与West的实验值符合得很好. 后一个化合物, 尚未见到动力学实验结果的报道. 本文指出了这类化合物构型熵贡献的重要性.

Transition state kinetic parameters calculation on cis-trans isomerization in disilene

The transition state theory approach to cis-trans isomerization in substituted disilenes is presented. The activation entropy of the isomerization and corresponding Arrhenius A-factor for these substituted disilenes such as 1,2-di-tert-butyl-1,2-dimesityldisilene, 1,2-bis[bis(trimethylsilyl)amino]-1,2-dimesityldisilene and 1,2-dimethyl-1,2-diphenyldisilene have been calculated The results of the first two compounds are in good agreement with those found experimental (M. J. Michalczyk et al., 1985). No experimental result was available for the third one. The structure-entropy for such kinds of compounds is important.