Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde
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- 作者：ZhiFeng Li (1)
YuanCheng Zhu (1)
Sheng Yang (1)
XiaoQuan Lu (2) - 关键词：CCl2 ; acetaldehyde ; insertion reaction ; DFT ; NBO ; AIM
- 刊名：Chinese Science Bulletin
- 出版年：2008
- 出版时间：August 2008
- 年：2008
- 卷：53
- 期：15
- 页码：2287-2296
- 全文大小：1851KB
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YuanCheng Zhu (1)
Sheng Yang (1)
XiaoQuan Lu (2)
1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui, 741001, China
2. Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, China - ISSN：1861-9541
文摘
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/6-1G(d). All the energy of the species was obtained at the CCSD(T)/6-1G(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 II). There are three main existing pathways and the products are P1 (CH3COHCCl2), P2 (CH2COHCHCl2) and P4[CHCl2CHCHOH] 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.