Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde

The insertion reaction mechanisms of siglet and striglet CCI2 with CH3CHO have been studied by using the DFT, NBO, CCSD（T） and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6-31G（d）. All the energy of the species was obtained at the CCSD（T）/6-31G（d,p） level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα--H （reaction I） but also can react with Cβ--H （reaction ll）. There are three main existing pathways and the products are P1 （CH3COHCCl2）, P2 （CH2COHCHCl2） and P4CHCl2CHCHOH] respectively. Reaction II happens more easily according to the energy changes and the barrier in rate-controlling step. In addition, the important geometries in domain pathways have been studied by AIM theory. And also, the energy changes of H in the inserted C--H bond have been investigated.

Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde

The insertion reaction mechanisms of siglet and striglet CCl₂ with CH₃CHO have been studied by using the DFT, NBO, CCSD(T) and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6–31G(d). All the energy of the species was obtained at the CCSD(T)/6–31G(d,p) level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl₂ can not only insert the C_α—H (reaction I) but also can react with C_β—H (reaction II). There are three main existing pathways and the products are P1 (CH₃COHCCl₂), P2 (CH₂COHCHCl₂) and P4CHCl₂CHCHOH] respectively. Reaction II happens more easily according to the energy changes and the barrier in rate-controlling step. In addition, the important geometries in domain pathways have been studied by AIM theory. And also, the energy changes of H in the inserted C—H bond have been investigated. Supported by the Foundation of Education Committee of Gansu Province (Grant No. 0708-11) and Foundation of Tianshui Normal University (Grant No. TSA0604)