Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (09): 2543-2548.doi: 10.3866/PKU.WHXB20100830

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

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).

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