【摘要】 该文在M06-2X/SMD/6-311+G（d, p）水平上，研究了在水溶剂环境1 atm压力和310.15 K温度下Eda酮式异构体与超氧负离子自由基O₂^-·的反应机理.研究发现：Eda酮式异构体与O₂^-·的反应有抽H、加成以及单电子转移3种方式.反应势能面研究表明：抽H反应的自由能垒为38.0～176.1 kJ·mol^-1,优势通道是O₂^-·抽取杂环H,反应能垒为38.0～41.0 kJ·mol^-1.加成反应的自由能垒为84.2～196.6 kJ·mol^-1,优势通道是O₂^-·加成到杂环与甲基相连的C原子上，反应能垒为84.2 kJ·mol^-1.单电子从Eda酮式异构体向O₂^-·转移的反应的能垒为409.2 kJ·mol^-1,该反应不能实现.研究结果表明：在水溶剂环境下Eda酮式异构体可通过提供杂环H以及甲基邻位C与自由基加成2种途径消除O₂^-·.更多还原

【Abstract】 At the level of M06-2X/SMD/6-311+G（d, p）,the reaction mechanism of Eda ketone isomer with superoxide anion radical O₂^-· is studied in aqueous solvent environment of 1 atmosphere pressure and 310.15 K temperature. The studies show that Eda ketone isomer reacts with O₂^-· in three ways that are H extraction, addition and single electron transfer.The study of reaction potential energy surface shows that the free energy barrier of H extraction is between 38.0 and 176.1 kJ·mol^-1.The dominant channel is extraction of heterocyclic H by O₂^-·,its reaction energy barrier is between 38.0 and 41.0 kJ·mol^-1.The free energy barrier of addition reaction is between 84.2 and 196.6 kJ·mol^-1,the dominant channel is the addition of O₂^-· to the heterocyclic C atom attached to the methyl group, and the reaction energy barrier is 84.2 kJ·mol^-1.The energy barrier of single electron transferring from Eda ketone isomer to O₂^-· is 409.2 kJ·mol^-1,this reaction cannot be realized.The results show that Eda ketone isomers can eliminate O₂^-· by providing heterocyclic H and adding methyl ortho-C with free radicals in aqueous solvent.更多还原