类锗烯H_2GeLiCl与RH(R=Cl,SH,PH_2)的插入反应

Insertion Reactions of the Germylenoid H_2GeLiCl with RH(R= Cl,SH,PH_2)

应用DFT B3LYP和QCISD方法研究类锗烯H2GeLiCl与RH(R=Cl,SH,PH2)的插入反应.在B3LYP/6-311+G(d,p)水平上优化反应势能面上所有驻点的构型,并用QCISD/6-311++G(d,p)方法计算单点能,并考察溶剂化效应对反应的影响.结果表明,类锗烯H2GeLiCl与RH(R=Cl,SH,PH2)插入反应势能面上存在1个过渡态(TS)和1个中间体(IM)连接反应物和产物.气相条件下,3个插入反应的势垒分别为93.47(R=Cl),133.32(R=SH)和212.25(R=PH2)kJ/mol,表明相同条件下发生插入反应时,反应活性由大到小的物质为H-Cl,H-SH,H-PH2;溶剂极性越大,插入反应越容易进行.

This article studies the insert reaction of germylenoid H2GeLiCl with RH （R= Cl, SH, PH2） with the methods of DFT B3LYP and QCISD. It optimizes the configuration of all stationary points onto the surface of reaction potential energy on the level of B3LYP/6-311 ＋G（d,p） and calculates single-point energy with the method of QCISD/6-311 ＋ ＋ G（d,p）, it also investigates the effect of solvent effect on reaction. The result shows that there is connected reactant and outcome of transition state （TS） and intermediate onto the insertion reaction potential energy surface of germylenoid H2GeLiC1 and RH （R= Cl, SH, PH2）. Each potential barrier of three insert reaction under gas phase condition is 93.47 （R= Cl）, 133.32 （R= SH）, and 212.25 （R= PH2） kJ/mol, which shows that the matters are H-Cl,H-SH, H-PH2 in descending reactivity order when insert reaction occurs under the same conditions. The more the solvent polarity is, the easier the insert reaction will be.