Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

• 来源期刊: 中国科学B辑（英文版）
• 年，卷（期）: 2009,（3）
• 页码范围: 304-312
• 页数: 9页
• 语种: 英文
• DOI: 10.1007/s11426-009-0060-9

摘要

The Insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6-311G(d, p). All the energy of the species was obtained at the CCSD(T)/6-311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH3OCHCl2, reaction I (1)], P3[Cl2HCCH2OH, reaction Ⅰ(2)], PS[CH3SCHCl2, reaction Ⅱ(1)] and P7[Cl2HCCH2SH, reac-tion Ⅱ(2)] are produced respectively, but also abstract M-H, resulting P4 [CH2O+CH2Cl2, reaction Ⅰ(3)] and PS[CH2S+CH2Cl2, reaction Ⅱ (3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.