物理化学学报 >> 2010, Vol. 26 >> Issue (09): 2543-2548.doi: 10.3866/PKU.WHXB20100830

量子化学及计算化学 上一篇    下一篇

三重态类硅烯HB=SiLiF的结构及其与R—H(R=F, OH, NH2)的插入反应

李文佐, 祝洪杰, 程建波, 李庆忠, 宫宝安   

  1. 烟台大学化学生物理工学院, 山东烟台264005
  • 收稿日期:2010-03-17 修回日期:2010-04-06 发布日期:2010-09-02
  • 通讯作者: 李文佐 E-mail:liwenzuo2004@126.com
  • 基金资助:

    山东省自然科学基金(ZR2009BQ006),超分子结构与材料国家重点实验室(吉林大学)开放基金(SKLSSM200909)和烟台大学博士科研基金(HY05B30, HY05B36)资助项目

Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH2)

LI Wen-Zuo, ZHU Hong-Jie, CHENG Jian-Bo, LI Qing-Zhong, GONG Bao-An   

  1. Chemistry and Biology College, Yantai University, Yantai 264005, Shandong Province, P. R. China
  • Received:2010-03-17 Revised:2010-04-06 Published:2010-09-02
  • Contact: LI Wen-Zuo E-mail:liwenzuo2004@126.com
  • Supported by:

    The project was supported by the Natural Science Foundation of Shandong Province, China (ZR2009BQ006), Open Fund of the State Key Laboratory of Supramolecular Structure and Materials (Jilin University, China) (SKLSSM200909), and Fund for Doctor of Yantai University, China (HY05B30,HY05B36).

摘要:

用密度泛函理论(DFT)和二次组态相互作用(QCISD)方法研究了三重态类硅烯HB=SiLiF 的结构及其 与RH (R=F, OH, NH2)的插入反应. 计算结果表明, 类硅烯HB=SiLiF有三种平衡构型, 其中四元环构型能量最 低, 是其存在的主要构型. HB=SiLiF 与HF, H2O和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124.85, 140.67和148.16 kJ·mol-1, 反应热分别为-2.22, 20.08 和23.22 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: 插入反应, 类硅烯HB=SiLiF, B3LYP, QCISD

Abstract:

Density functional theory (DFT) and quadratic configuration interaction with single and double excitations (QCISD) methods were used to investigate the geometries of the triplet silylenoid HB=SiLiF as well as its insertion reactions with RH (R=F, OH, NH2). The calculated results indicated that HB=SiLiF has three equilibrium structures wherein the four-membered ring structure had the lowest energy and it was the most stable structure. The mechanisms of the insertion reactions for HB=SiLiF with HF, H2O, and NH3 were identical. The QCISD/6-311++G(d,p)//B3LYP/ 6-311+G(d,p) calculated potential energy barriers of the three reactions were 124.85, 140.67, and 148.16 kJ·mol-1, and the reaction heats for the three reactions were -2.22, 20.08, and 23.22 kJ·mol -1, respectively. Under the same conditions, the insertion reactions should occur easily according to the following order: H—F>H—OH>H—NH2.

Key words: Insertion reaction, Silylenoid HB=SiLiF, B3LYP, QCISD