Diels鈥揂lder Reactions of Graphene: Computational Predictions of Products and Sites of Reaction

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• 作者：Yang Cao ; S铆lvia Osuna ; Yong Liang ; Robert C. Haddon ; K. N. Houk
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：November 20, 2013
• 年：2013
• 卷：135
• 期：46
• 页码：17643-17649
• 全文大小：491K
• 年卷期：v.135,no.46(November 20, 2013)
• ISSN：1520-5126

文摘

The cycloaddition reactions and noncovalent 蟺 interactions of 2,3-dimethoxybutadiene (DMBD), 9-methylanthracene (MeA), tetracyanoethylene (TCNE), and maleic anhydride (MA) with graphene models have been investigated using density functional theory (DFT) calculations. Reaction enthalpies have been obtained to assess the reactivity and selectivity of covalent and noncovalent functionalization. Results indicate that graphene edges may be functionalized by the four reagents through cycloaddition reactions, while the interior regions cannot react. Noncovalent complexation is much more favorable than cycloaddition reactions on interior bonds of graphene. The relative reactivities of different sites in graphene are related to loss of aromaticity and can be predicted using H眉ckel molecular orbital (HMO) localization energy calculations.