硫醚与2-甲基-1,5-己二烯反应的机理研究
Theoretical study on the mechanism of the reaction between thioether and 2-methyl-1,5-hexadiene
李青益 1石云 1刘国魁 1冷霞 1李云志 1韦瑶瑶 1王佳褀 1周慧敏 1周广丽 1夏其英1
作者信息
- 1. 临沂大学化学化工学院,临沂 276000
- 折叠
摘要
采用密度泛函理论对硫醚与2-甲基-1,5-己二烯的反应机理进行了详细的理论探究.计算结果表明,该反应历程主要包含活性物种的生成、2-甲基-1,5-己二烯的插入、另一分子的硫醚的碳氢键活化三部分.在2-甲基-1,5-己二烯插入步骤中,发现其采用6-5-re-插入时需要克服的活化能垒最低,反应时更为占优,在进行烯烃分子内碳碳双键插入完成闭环反应时相对比较容易.通过能量对比探明硫醚的C-H键活化需要克服的能垒最高,为该反应的速控步.
Abstract
In this paper,the mechanism of the reaction between thioether and 2-methyl-1,5-hexadiene was investigated in detail by using density functional theory.The calculation results show that the reaction process mainly includes three parts:the generation of the three-membered metallacycle active species,the insertion of 2-methyl-1,5-hexadiene,and the subsequent C-H activation of another molecule of thioether.In the process of 2-methyl-1,5-hexadiene insertion,it is suitable for more favorable a 6-5-re-face insertion due to the lower energy barrier,and it is relatively easy to complete the closed-loop reaction followed by the in-sertion of the carbon-carbon double bond.The whole reaction process is controlled by C-H activation step ow-ing to the highest energy barrier.
关键词
稀土金属配合物/碳氢键活化/密度泛函理论Key words
Rare-earth metal complex/C-H activation/Density functional theory引用本文复制引用
基金项目
临沂大学2022年度大学生创新训练项目(X202210452415)
出版年
2024
国家科技期刊平台
NSTL
维普
万方数据