| 引用本文格式: 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. Theoretical Study on the mechanism of the reaction between thioether and 2-methyl-1, 5-hexadiene [J]. J. At. Mol. Phys., 2024, 41(3): 031006 (in Chinese) [李青益,石云,刘国魁,冷霞,李云志,韦瑶瑶,王佳琪,周慧敏,周广丽,夏其英. 硫醚与2-甲基-1,5-己二烯反应的机理研究 [J]. 原子与分子物理学报, 2024, 41(3): 031006] |
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| 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 |
| 摘要点击 166 全文点击 28 投稿时间：2022-11-23 修订日期：2022-12-06 |
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| DOI编号
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| 中文关键词
稀土金属配合物 碳氢键活化 密度泛函理论 |
| 英文关键词
Rare-earth metal complex C-H activation Density functional theory |
| 基金项目
国家自然科学基金 |
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| 中文摘要
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| 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。 |
| 英文摘要
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| 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. |
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