Citation: WANG Yan, ZENG Xiao-Lan. 1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH₂)[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201208134 shu

1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH₂)

WANG Yan ,
ZENG Xiao-Lan

1.
College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, Henan Province, P. R. China

Received Date: 20 June 2012
Available Online: 13 August 2012
Fund Project: 河南省基础与前沿技术研究计划(092300410207)资助项目 (092300410207)

Density functional theory calculations at the B3LYP/6-311 ++ G(d,p) level were performed to study the reaction mechanism and potential energy surface of the 1,2- and 1,4-addition reactions between silabenzenes and HX (X=F, OH, NH₂). The influences of substituents at the Si atom and tetrahydrofuran as a solvent on the potential energy surfaces of the reactions were also explored. The results indicated that the title reactions occur by the following two mechanisms: (1) silabenzene and one HX molecule form an intermediate complex, and then isomerize to give final product via a four-membered transition state; and (2) silabenzene and two HX molecules form an intermediate complex, and then isomerize via a sixmembered transition state to give another intermediate complex from which one HX molecule is left to afford the final product. Mechanism 2 is much more favorable than mechanism 1 kinetically. The preference for the 1,2- or 1,4-addition product is determined by kinetics and is related to the X group. The reactivity order of HX toward the addition reaction with silabenzene in gas phase is HF>H₂O>NH₃. Strong electron-donating and -withdrawing substituents at the Si atom have a favorable influence on the potential energy surfaces of the 1,2- and 1,4-addition reactions, while the large mesityl group has the opposite effect. Tetrahydrofuran has an unfavorable thermodynamic influence on the reactions, and kinetically on those reactions with HF or H₂O. However, it favors the reactions between silabenzenes and NH3 kinetically.
- Density functional theory,
- Silabenzene,
- Addition reaction,
- Reaction mechanism
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沈阳化工大学材料科学与工程学院沈阳 110142

1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH2)

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1,2- and 1,4-Addition Reactions between Silabenzenes and HX (X=F, OH, NH₂)