| BF_3活化高锰酸氧化丙烯酸反应机理的密度泛函研究 |
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| 引用本文： | 张兴辉,耿志远.BF_3活化高锰酸氧化丙烯酸反应机理的密度泛函研究[J].中国科学:化学,2010(4). |
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| 作者姓名： | 张兴辉 耿志远 |
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| 作者单位： | 甘肃联合大学化工学院;西北师范大学化学化工学院;甘肃省高分子材料重点实验室; |
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| 基金项目： | 甘肃省自然科学基金资助(0720kJZA114) |
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| 摘 要： | 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.
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| 关 键 词： | 环加成 BF3活化 高锰酸根离子 密度泛函理论 |
Density functional study on the mechanism of BF_3-activated oxidation of alkenes by MnO_4~- |
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| ZHANG XingHui & GENG ZhiYuan College of Chemical Engineering,Gansu Lianhe University,Lanzhou ,China, College of Chemistry , Chemical Engineering,Key Laboratory of Polymer Materials of Gansu Province,Northwest Normal University,Lanzhou.Density functional study on the mechanism of BF_3-activated oxidation of alkenes by MnO_4~-[J].Scientia Sinica Chimica,2010(4). |
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| Authors: | ZHANG XingHui & GENG ZhiYuan College of Chemical Engineering Gansu Lianhe University Lanzhou China College of Chemistry Chemical Engineering Key Laboratory of Polymer Materials of Gansu Province Northwest Normal University Lanzhou |
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| Institution: | ZHANG XingHui1 & GENG ZhiYuan2 1 College of Chemical Engineering,Gansu Lianhe University,Lanzhou 730010,China,2 College of Chemistry , Chemical Engineering,Key Laboratory of Polymer Materials of Gansu Province,Northwest Normal University,Lanzhou 730070 |
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| Abstract: | A computational study of the Cycloaddition reactions of permanganate ion with acrylic acid is presented.The reaction proceeds through two competing channels:2+3 and 2+2 pathway.The accelerating effect for the reaction systems was investigated by explicit coordination of the BF3 molecules to the oxygen atoms in the permanganate ion.The barriers for the 2+3 pathway become systematically lower as more BF3 molecules are added(from 36.44 kJ/mol for no BF3 molecules to 23.97 kJ/mol for two BF3 molecules).The reac... |
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| Keywords: | cycloaddition BF3-activated permanganate ion density functional theory |
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