物理化学学报 >> 2008, Vol. 24 >> Issue (04): 720-724.doi: 10.3866/PKU.WHXB20080431

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类锗烯H2C=GeLiCl与RH(R=F, OH, NH2)的插入反应

李文佐; 肖翠平; 宫宝安; 程建波   

  1. 烟台大学化学生物理工学院, 山东 烟台 264005; 吉林大学超分子结构与材料教育部重点实验室, 长春 130012
  • 收稿日期:2007-10-11 修回日期:2008-01-10 发布日期:2008-04-07
  • 通讯作者: 李文佐 E-mail:liwenzuo2004@126.com

Insertion Reactions of the Germylenoid H2C=GeLiCl with RH(R=F, OH, NH2)

LI Wen-Zuo; XIAO Cui-Ping; GONG Bao-An; CHENG Jian-Bo   

  1. Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, Shandong Province, P. R. China; Key Laboratory for Supramolecular Structure and Materials of the Ministry of Education, Jilin University, Changchun 130012, P. R. China
  • Received:2007-10-11 Revised:2008-01-10 Published:2008-04-07
  • Contact: LI Wen-Zuo E-mail:liwenzuo2004@126.com

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摘要： 采用DFT B3LYP和QCISD方法研究了不饱和类锗烯H2C=GeLiCl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=GeLiCl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173.53、194.48和209.05 kJ·mol-1, 反应热分别为60.18、72.93和75.34 kJ·mol-1. 相同条件下发生插入反应时, 反应活性顺序都是H—F>H—OH>H—NH2.

关键词: 类锗烯H2C=GeLiCl, RH(R=F, OH, NH2), 插入反应, DFT, QCISD

Abstract: The insertion reactions of the germylenoid H2C=GeLiCl with RH(R=F, OH, NH2) were studied 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. The calculated results indicated that the mechanisms of the insertion reactions of H2C=GeLiCl with HF, H2O, and NH3 were 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 were 173.53, 194.48, and 209.05 kJ·mol-1, and the reaction energies for the three reactions were 60.18, 72.93, and 75.34 kJ·mol-1, respectively. Under the same situation, the insertion reactions should occur easily in the following order: H—F>H—OH>H—NH2.

Key words: Germylenoid H2C=GeLiCl, RH(R=F, OH, NH2), Insertion reaction, DFT, QCISD