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

Abstract

The insertion and abstraction reaction mechanisms of singlet and triplet CCl 2 with CH 3 MH (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 CCl 2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH 3 OCHCl 2 , reactionⅠ(1)], P3[Cl 2 HCCH 2 OH, reactionⅠ(2)], P5[CH 3 SCHCl 2 , reactionⅡ(1)] and P7[Cl 2 HCCH 2 SH, reaction Ⅱ(2)] are produced respectively, but also abstract M-H, resulting P4 [CH 2 O+CH 2 Cl 2 , reactionⅠ(3)] and P8[CH 2 S+CH 2 Cl 2 , reactionⅡ(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.