Qi Yuhua, Xu Chongjuan, Geng Bing, He Maoxia
Key Laboratory of Fluorine Chemistry and Chemical Materials of Shandong Province, School of Chemistry and Chemical Engineering, University of Jinan, Jinan, 250022, People's Republic of China,
J Mol Model. 2014 Nov;20(11):2462. doi: 10.1007/s00894-014-2462-7. Epub 2014 Oct 16.
The structures and stabilities of RBrSiLi2 (R=CH3, C(SiH3)3) have been studied using ab initio and DFT methods. CH3BrSiLi2 and C(SiH3)3BrSiLi2 have three possible structures, the p-complex, the plain, and the folded structures. The plain and the folded structures are different from those of known structures of silylenoids. The energy of the plain structure is the lowest and nearly equals to that of the folded structure. The plain and the folded structures, which can isomerize into each other, are the most stable and possibly detected ones in chemical reactions. The essential of the insertion reactions with Me3SiCl is the same. The insertion barriers are in the order of H2SiLiBr > C(SiH3)3BrSiLi2 > CH3BrSiLi2. The C(SiH3)3 group makes the insertion of C(SiH3)3BrSiLi2 more difficult.
已使用从头算和密度泛函理论方法研究了RBrSiLi2（R = CH3，C(SiH3)3）的结构和稳定性。CH3BrSiLi2和C(SiH3)3BrSiLi2有三种可能的结构，即π-络合物结构、平面结构和折叠结构。平面结构和折叠结构与已知硅烯类似物的结构不同。平面结构的能量最低，且几乎与折叠结构的能量相等。平面结构和折叠结构可以相互异构化，它们是化学反应中最稳定且可能被检测到的结构。与Me3SiCl发生插入反应的本质相同。插入势垒的顺序为H2SiLiBr > C(SiH3)3BrSiLi2 > CH3BrSiLi2。C(SiH3)3基团使C(SiH3)3BrSiLi2的插入更加困难。
