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利用密度泛函和自然键轨道理论及电子密度拓扑分析方法,对单、三重态CCl2与CH3MH(M=O,S)中C—H和M—H键的插入反应及抽提氢反应进行了研究.在B3LYP/6-311G(d,p)水平上优化了势能面上构型,并以频率分析和内禀反应坐标法进行了确认.计算了各物种的CCSD(T)/6-311G(d,p)能量.结果表明,主反应通道主要发生在单重态势能面中,单重态CCl2既可以与C—H及M—H键发生插入反应,存在四条主反应通道,分别生成P1[CH3OCHCl2,反应Ⅰ(1)],P3[Cl2HCCH2OH,反应Ⅰ(2)]和P5[CH3SCHCl2,反应Ⅱ(1)],P7[Cl2HCCH2SH,反应Ⅱ(2)],也可以与CH3MH发生抽提氢反应,分别生成P4[CH2O+CH2Cl2,反应Ⅰ(3)]和P8[CH2S+CH2Cl2,反应Ⅱ(3)].同时,存在三重态CCl2与CH3SH插入生成3P4[CH3SCHCl+Cl]的反应通道.进一步对反应通道上的关键点进行了自然键轨道和电子密度拓扑分析.
The insertion reaction and hydrogen extraction of C-H and M-H bonds in single and triplet CCl2 and CH3MH (M = O, S) were carried out using density functional theory, natural bond orbital theory and electron density topological analysis The configuration of the potential energy plane was optimized at B3LYP / 6-311G (d, p) level and was confirmed by frequency analysis and intrinsic reaction coordinate method.The CCSD (T) / 6-311G (d, p) energy.The results show that the main reaction channel mainly occurs in the singlet potential energy surface, and the singlet CCl2 can intercalate with the C-H and M-H bonds and there are four main reaction channels to generate P1 [CH3OCHCl2, reaction I (1)], P3 [Cl2HCCH2OH, reaction I (2)] and P5 [CH3SCHCl2, reaction II (1)], P7 [Cl2HCCH2SH, reaction II (2)] or CH3MH (3)] and P8 [CH2S + CH2Cl2, reaction Ⅱ (3)] respectively. At the same time, the existence of triplet CCl2 and CH3SH insertion into the reaction channel of 3P4 [CH3SCHCl + Cl] The key points of the reaction channel were further analyzed by natural bond orbital and electron density topological analysis.