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

• 来源期刊: 科学通报（英文版）
• 年，卷（期）: 2008,（15）
• 页码范围: 2287-2296
• 页数: 10页
• 语种: 英文
• DOI: 10.1007/s11434-008-0312-7

摘要

The insertion reaction mechanisms of siglet and striglet CCI2with 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 CCI2can not only insert the Cα--H (reaction Ⅰ) but also can react with Cβ--H (reaction Ⅱ). There are three main existing pathways and the products are P1 (CH3COHCCI2), P2 (CH2COHCHCI2) and P4[CHCI2CHCHOH] 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.