二溴卡宾与CH_3OH多通道反应的理论计算

Theoretical study on the multi-channel reaction mechanism of CBr_2 with CH_3OH

对单、三重态CBr_2与CH_3OH的多通道反应进行了理论计算.在B3LYP/6-311G*水平上优化了势能面上构型并进行了构型确认.计算了各物种经零点能校正的CCSD(T)能量.结果表明,单重态CBr_2既可以与O—H键插入生成1,1-二溴代甲醚P1(CH_3OCHBr_2),也可以与C—H键插入生成2,2-二溴代乙醇P3(Br_2HCCH_2OH).同时,存在单重态CBr_2与CH_3OH抽提双氢生成P_(abs)(CH_2O+CH_2Br_2)的反应.采用统计热力学及Wigner校正的Erying理论研究了主反应通道的热力学及动力学性质,并对反应通道上的关键点进行了NBO和AIM分析.

The reaction mechanism of singlet and triplet CBr2 with CH3 OH has been studied by using the B3LYP/ 6-311G＊ and CCSD（T） theory. The calculations indicated that major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr2 can not only trigger insertion reaction with C-H and O-H, by which the products P1 [CH3OCHBr2 ] and P3[Br2 HCCH2 OH] are produced respectively, but also abstract O-H, resulting Pabs[CH2O＋CH2Br2]. The statistical thermody- namics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.