At the level of M06-2X/SMD/6-311+G(d,p),the reaction mechanism of Eda ketone isomer with super-oxide anion radical O2-·is studied in aqueous solvent environment of 1 atmosphere pressure and 310.15 K temper-ature.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 extrac-tion is between 38.0 and 176.1 kJ·mol-1.The dominant channel is extraction of heterocyclic H by O2-·,its reac-tion 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.
万方数据