Diels?Alder Cycloaddition of Cyclopentadiene and C60 at the Extreme High Pressure
Diels?Alder Cycloaddition of Cyclopentadiene and C60 at the Extreme High Pressure
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环戊二烯和 C60 在极高压下的 Diels?Alder 环加成反应
DOI：
10.1021/acs.jpca.7b02805
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Ehara Masahiro
中科院分区：
文献类型：
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作者：
Yang Tao;Fukuda Ryoichi;Cammi Roberto;Ehara Masahiro
富勒烯高压Diels-Alder环加成反应是制备热稳定环加合物的重要方法。采用极压极化连续体模型（XP-PCM）研究了高压对环戊二烯和c60的Diels-Alder环加成反应势能面的影响。结果表明，高压使反应活化能大幅度降低，反应能大幅度提高，有利于DA反应的进行。压力对反应能量的影响可分为空化贡献和电子贡献。对于活化能，空化的贡献比电子的贡献更显著。为了方便以后的实验，根据活化能或反应能与压力的线性关系拟合出活化能或反应能与压力的关系，计算活化能和反应体积。
High-pressure Diels–Alder cycloaddition reaction of fullerenes is an important synthetic method for the thermally stable cycloadducts. The effects of high pressure on the potential energy surfaces of Diels–Alder cycloaddition of cyclopentadiene and C60were studied with a recently developed approach, the polarizable continuum model for extreme pressure (XP-PCM). It is revealed that the high pressure reduces the activation energies and increases reaction energies drastically, making the DA reaction more favorable. The pressure effects on the reaction energetics can be divided into the cavitation and electronic contributions. For the activation energy, the cavitation contribution is significant in comparison with the electronic contribution. To assist future experiments, the activation volume and reaction volume were computed on the basis of the relationship between activation energy or reaction energy with the pressure as a consequence of the fitting linear correlation between activation energy or reaction energy with the pressure.