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

doi:10.3866/PKU.WHXB20100830

Abstract

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

LI Wen-Zuo,ZHU Hong-Jie, CHENG Jian-Bo, LI Qing-Zhong, GONG Bao-An. Structures of the Triplet Silylenoid HB=SiLiF and Its Insertion Reactions with R—H(R=F, OH, NH₂)[J].Acta Phys. -Chim. Sin., 2010, 26(09): 2543-2548.

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

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

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