QUANTUM MECHANICAL STUDY OF THE INSERTION REACTION BETWEEN CYCLOPROPENYLIDENE WITH R-H (R=F, OH, NH2, CH3)

Journal of The Chilean Chemical Society

LIU, HUI¹  TAN, XIAOJUN¹  JING, YING²  CHEN, YUNGANG³  YU, YANG³  ZHANG, YONGLING³  GU, JINSONG³  WANG, HAILONG³ 

[1] Shandong Academy of Medical Sciences, Jinan, People's Republic of China;The General Hospital of Jinan Military Command, Jinan, People's Republic of China;University of Jinan, Jinan, People's Republic of China

关键词: Carbene;    Cyclopropenylidene;    Reaction mechanism;    MP2 method.;   

DOI  :  10.4067/S0717-97072013000400068

学科分类：化学（综合）

来源: Sociedad Chilena de Quimica

【 摘 要 】

To further reveal the reactivityof cyclopropenylidene with R-H compounds, mechanisms of four reactions betweencyclopropenylidene and R-H (R=F, OH, NH2, CH3) havebeen systematically investigated employing the second-order Møller-Plessetperturbation theory (MP2) method. Geometry optimization, vibrational analysis,and energy property for the involved stationary points on the potential energysurface have been calculated. All the mechanisms of four reactions are identicalto each other. Based on the calculated results, there are three steps (stepa, b, and c) along the reaction between cyclopropenylidene and R-H. Forthe first step, cyclopropenylidene is inserted into R-H to form an three-memberedring intermediate. For the second step, the three-membered ring is openedto form a carbene intermediate. With regard to the third step, it is H-transferedprocesses, the ultimate product is alkyne.

【 授权许可】

Unknown