Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, People's Republic of China.
J Mol Model. 2012 Mar;18(3):1015-21. doi: 10.1007/s00894-011-1129-x. Epub 2011 Jun 10.
The insertion reactions of the silylenoid H(2)SiLiF with SiH(3)XH(n-1) (X = F, Cl, Br, O, N; n = 1, 1, 1, 2, 3) have been studied by DFT calculations. The results indicate that the insertions proceed in a concerted manner, forming H(3)SiSiH(2)XH(n-1) and LiF. The essence of H(2)SiLiF insertion into Si-X bonds reactions are the donations of the electrons of X into the p orbital on the Si atom in H(2)SiLiF and the σ electrons on the Si atom in H(2)SiLiF to the positive SiH(3) group. The order of reactivity by H(2)SiLiF insertion in vacuum indicates the reaction barriers decrease for the same-row element X from right to left and the same-family element X from up down in the periodic table. The insertion reactions in ether are similar to those in vacuum. The energy barriers in vacuum are higher than those in ether. The silylenoid insertions are thermodynamically exothermic both in vacuum and in ether.
硅烯 H(2)SiLiF 与 SiH(3)XH(n-1)（X= F、Cl、Br、O、N；n=1、1、1、2、3）的插入反应已通过 DFT 计算进行了研究。结果表明，插入反应以协同方式进行，形成 H(3)SiSiH(2)XH(n-1)和 LiF。H(2)SiLiF 插入 Si-X 键反应的本质是 X 原子上的电子向 H(2)SiLiF 中 Si 原子的 p 轨道和 H(2)SiLiF 中 Si 原子上的σ电子捐赠到正 SiH(3)基团。H(2)SiLiF 在真空中的插入反应活性顺序表明，同一列元素 X 从右到左，周期表中同族元素 X 从上到下，反应势垒降低。醚中的插入反应与真空中的反应相似。真空中的能垒高于醚中的能垒。硅烯插入在真空中和醚中都是热力学放热的。
