Theoretical study on the mechanism of substitution and insertion reactions between H2SiLiF and GeH3F

• 作 者: YanBing-Fei;ZhuYa-Nan;LiWen-Zuo;
• 机 构: College of Chemistry and Chemical Engineering,Yantai University,Yantai 264005,China
• 出 处: 第十二届全国量子化学会议
• 发表日期: 2014年期

　　Theoretical investigations on the mechanism of the substitution and insertion reactions of the three-membered-ring silylenoid H2SiLiF with GeH3F have been carried out by DFT calculations.The geometries of all the stationary points along the potential energy surfaces were optimized using the B3LYP method and then the QCISD method was used to calculate the single-point energies.The results indicated that the substitution reaction proceed via two reaction paths(path Ⅰ and Ⅱ).In each pathway,there were one precursor complex,one transition state,and one intermediate,which connected the reactants and the products.Considering the energy of precursor complex in substitution reaction(-84.41 kJ/mol)is much lower than that in insertion reaction(-6.39 kJ/mol),the substitution reaction occurs more readily.The potential energy barrier in path Ⅱ(23.62 kJ/mol)is lower than that of path I(48.49 kJ/mol),therefore path Ⅱ is the most favorable pathway.All substitution and insertion reactions of H2SiLiF with GeH3F are exothermic.The solvent effect on these reactions was discussed.In different solvent,path Ⅱ is still the most favorable pathway.