标题：Theoretical studies on the pentacoordinate silylenoid PhCH2(NH2)CH3SiLiF
作者：Qi, YH;Mu, ZG;Feng, DC
作者机构：[Qi, Y] School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China;[ Mu, Z] School of Chemistry and Chemical Engineering, 更多
通讯作者地址：[Qi, YH]Univ Jinan, Sch Chem & Chem Engn, Jinan 250022, Peoples R China.
关键词：DFT;Pentacoordinate silylenoids;Solvent effects
摘要：The structures of pentacoordinate silylenoid PhCH2(NH2)CH3SiLiF were studied by density functional theory at the B3LYP/6-31G(d) level. Three equilibrium structures, the three-membered ring (1), the p-complex (2), and the sigma-complex (3) structures, were located. Their energies are in the order of 2 > 1 > 3 both in vacuum and in THF. To exploit the stability of PhCH2(NH2)CH3SiLiF, the insertion reactions of 1 and PhCH2(NH2)CH3Si into C-F have been investigated, respectively. The results show that the insertion of PhCH2(NH2)CH3Si is more favorable. To probe the influence of amine-coordination to the stability of PhCH2(NH2)CH3SiLiF, the insertion reaction of PhCH3CH3SiLiF was also investigated. The calculations indicate that the insertion of PhCH3CH3SiLiF is more favorable than that of 1. So the N atom plays an important role on the stability of silylenoid PhCH2(NH2)CH3SiLiF.