The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, People's Republic of China.
J Mol Model. 2013 Oct;19(10):4537-43. doi: 10.1007/s00894-013-1970-1. Epub 2013 Aug 16.
A combined density functional and ab initio quantum chemical study of the insertion reactions of the germylenoid H2GeLiF with SiH3X (X = F, Cl, Br) was carried out. The geometries of all the stationary points of the reactions were optimized using the DFT B3LYP method and then the QCISD method was used to calculate the single-point energies. The theoretical calculations indicated that along the potential energy surface, there were one precursor complex (Q), one transition state (TS), and one intermediate (IM) which connected the reactants and the products. The calculated barrier heights relative to the respective precursors are 102.26 (X = F), 95.28 (X = Cl), and 84.42 (X = Br) kJ mol(-1) for the three different insertion reactions, respectively, indicating the insertion reactions should occur easily according to the following order: SiH3-Br > SiH3-Cl > SiH3-F under the same situation. The solvent effects on the insertion reactions were also calculated and it was found that the larger the dielectric constant, the easier the insertion reactions. The elucidations of the mechanism of these insertion reactions provided a new reaction model of germanium-silicon bond formation.
采用密度泛函理论（DFT）中的 B3LYP 方法和从头算量子化学（QCISD）方法相结合，对亚锗烯 H2GeLiF 与 SiH3X（X= F、Cl、Br）的插入反应进行了研究。所有反应的驻点几何结构均采用 DFT B3LYP 方法进行优化，然后采用 QCISD 方法计算单点能。理论计算表明，沿势能面存在一个前体复合物（Q）、一个过渡态（TS）和一个中间体（IM），它们连接反应物和产物。计算得到的相对于各前体的势垒高度分别为 102.26（X= F）、95.28（X= Cl）和 84.42（X= Br）kJ mol-1，这三个不同的插入反应分别表明，在相同条件下，插入反应应按以下顺序容易发生：SiH3-Br > SiH3-Cl > SiH3-F。还计算了插入反应的溶剂效应，发现介电常数越大，插入反应越容易。对这些插入反应机理的阐明提供了一种新的锗-硅键形成反应模型。
