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用量子化学密度泛函理论(DFT)的B3LYP方法对高锰酸根离子与丙烯酸的环加成反应机理进行了系统研究,全参数优化了反应势能面上各驻点的几何构型、振动频率和能量.计算结果表明:反应有两个竞争通道,即[2+3]反应通道和[2+2]反应通道,其中[2+3]通道比[2+2]通道的反应势垒降低了183.89kJ/mol,并通过在高锰酸根的氧原子上配位一个或两个BF3分子来研究BF3分子对反应体系的活化效应,结合两个BF3分子使得[2+3]通道的反应势垒降低为23.97kJ/mol,则有利于反应按该通道进行,然而[2+2]通道的反应势垒仍较高(>195kJ/mol).这进一步表明该反应体系中加入一定量BF3能提高高锰酸氧化烯烃双键的化学活性.
The B3LYP method of quantum chemical density functional theory (DFT) was used to systematically study the cycloaddition reaction between permanganate ion and acrylic acid. All the parameters optimize the geometrical configuration, vibrational frequency, Energy. The calculated results show that there are two competing channels: [2 + 3] and [2 + 2], in which the reaction barrier of [2 + 3] 183.89 kJ / mol, and the activation of BF3 molecule on the reaction system was studied by coordinating one or two BF3 molecules on the peroxynitrite of permanganate. Combining the two BF3 molecules, the reaction barrier of [2 + 3] channel To 23.97kJ / mol, it is in favor of the reaction according to the channel, however, the reaction barrier of [2 + 2] channel is still high (> 195kJ / mol), which further indicates that adding a certain amount of BF3 in the reaction system can improve Chemical activity of permanganic olefin oxide double bond.