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

作　　者：李青益 石云 刘国魁 冷霞 李云志 韦瑶瑶 王佳祺 周慧敏 周广丽 夏其英 LI Qing-Yi;SHI Yun;LIU Guo-Kui;LENG Xia;LI Yun-Zhi;WEI Yao-Yao;WANG Jia-Qi;ZHOU Hui-Min;ZHOU Guang-Li;XIA Qi-Ying(School of Chemistry and Chemical Engineering,Linyi University,Linyi 276000,China)

机构地区：[1]临沂大学化学化工学院,临沂276000

出　　处：《原子与分子物理学报》2024年第3期41-44,共4页Journal of Atomic and Molecular Physics

基　　金：临沂大学2022年度大学生创新训练项目(X202210452415)。

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.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 insertion of the carbon-carbon double bond.The whole reaction process is controlled by C-H activation step owing 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 

分 类 号：O64[理学—物理化学]