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用量子化学B3LYP/6-31G*方法研究了GaCl3催化下1,6-烯炔骨架重组生成1-乙烯基环戊烯的反应机理. 计算得到了该反应的反应物、过渡态及产物的几何优化构型及各驻点的能量, 进行了振动频率计算, 所有的过渡态都通过振动分析和IRC计算而得以确认. 结果表明: 反应分多步进行, 每步的活化能垒都较低; 整个反应过程主要是通过形成含有三中心两电子键的三元环状区域完成的; 反应具有明显的立体选择性, 顺式构型的1,6-烯炔将主要生成顺式构型的1-乙烯基环戊烯, 与实验现象完全吻合.
The reaction mechanism of 1-vinylcyclopentene with 1,6-alkynyl skeleton catalyzed by GaCl3 was studied by means of quantum chemical B3LYP / 6-31G * method.The reactants, transition states and geometries of the products The vibrational frequencies were calculated and all the transition states were confirmed by vibration analysis and IRC calculation.The results showed that the reactions were divided into several steps and the activation energy barriers were lower for each step. The whole reaction process is mainly through the formation of a three-center three-electron ring bond containing three ring-shaped region completed; the reaction has obvious stereoselectivity, the cis-configuration of 1, 6-ene alkyne will produce mainly cis configuration 1 - vinylcyclopentene, and the experimental phenomenon exactly.