硫醚与2-甲基-1,5-己二烯反应的机理研究

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.

Theoretical Study on the mechanism of the reaction between thioether and 2-methyl-1, 5-hexadiene

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.