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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (8): 756-760. 上一篇    下一篇

研究论文

类硅烯H2C＝SiLiBr与RH (R＝F, OH, NH2)的插入反应

李文佐*,a 程建波*,a 宫宝安a 于健康a,b 孙家钟a,b

  

  1. (a烟台大学化学生物理工学院 烟台 264005)
    (b吉林大学理论化学计算国家重点实验室 长春 130012)

  • 投稿日期:2008-01-23 修回日期:2008-10-10 发布日期:2009-04-28
  • 通讯作者: 李文佐

Insertion Reactions of the Silylenoid H2C＝SiLiBr to RH (R＝F, OH, NH2)

Li, Wenzuo *,a Cheng, Jianbo *,a Gong, Baoan a Yu, Jiankang a,b Sun, Jiazhong a,b

  

  1. (a Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005)
    (b State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130021)
  • Received:2008-01-23 Revised:2008-10-10 Published:2009-04-28
  • Contact: Li, Wenzuo

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采用DFT B3LYP和QCISD方法研究了类硅烯H2C＝SiLiBr与RH (R＝F, OH, NH2)的插入反应. 在B3LYP/6- 311＋G(d,p)水平上优化了反应势能面上的驻点构型. 结果表明, H2C＝SiLiBr与HF, H2O或NH3发生插入反应的机理相同. QCISD/6-311＋＋G(d,p)//B3LYP/6-311＋G(d,p)计算的三个反应的势垒分别为148.62, 164.42和165.07 kJ•mol－1, 反应热分别为－69.63, －43.02和－28.27 kJ•mol－1. 相同条件下发生插入反应时, 反应活性都是H—F＞H—OH＞H—NH2.

关键词: 类硅烯H2C＝SiLiBr, RH (R＝F, OH, NH2), 插入反应, DFT, QCISD

The insertion reactions of the silylenoid H2C＝SiLiBr to RH (R＝F, OH, NH2) were studied by using the DFT B3LYP and QCISD methods. The geometries of the stationary points on the potential energy surfaces of the reactions were optimized at the B3LYP/6-311＋G (d,p) level of theory. The calculated results indicate that the mechanisms of the insertion reactions of H2C＝SiLiBr to HF, H2O, and NH3 are identical to each other. The QCISD/6-311＋＋G(d,p)//B3LYP/6-311＋G(d,p) calculated potential energy barriers of the three reactions are 148.62, 164.42, and 165.07 kJ/mol, and the reaction energies for the three reactions are －69.63, －43.02, and －28.27 kJ/mol, respectively. Under the same situation, the insertion reactions should occur easily in the following order H—F＞H—OH＞H—NH2.

Key words: silylenoid H2C＝SiLiBr, RH (R＝F, OH, NH2), insertion reaction, DFT, QCISD