Comparative Computational Study of Hydrogen Abstraction Reactions of CY3H + XO− (X, Y = F, Cl, and Br)

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• 作者：Liang Junxi ; Su Qiong ; Zhao Dezhi ; Wang Yanbin ; Li Guihua and Geng Zhiyuan
• 刊名：Heteroatom Chemistry
• 出版年：2016
• 出版时间：July 2016
• 年：2016
• 卷：27
• 期：4
• 页码：199-209
• 全文大小：643K
• ISSN：1098-1071

文摘

The effects of halogen substituents on the reactivity are characterized by the hybrid B3LYP and BHandHLYP functionals of density functional theory using the aug-cc-pVDZ basis set. The species XO⁻ and CY₃H, where X, Y = F, Cl, and Br, have been chosen as model reactants in this work. Also, the mechanism of the hydrogen abstraction (HAT) reaction has been used to study the chemical reactivity of these anionic reactions. Our theoretical findings suggest that the relative reactivity of the CY₃H + XO⁻ reactions increases as Y goes from F to Br and decreases as X goes from F to Br. Moreover, among all reactions investigated in this study, the special role of the Y has very dominant effect on activation of the C–H bond in CY₃H when XO⁻ attacks the CY₃H. Again, through the transition state theory the rate constants at 298–1000 K are also evaluated for the HAT reactions, indicating the lower the temperature the faster is the chemical reaction.