Citation: Li Qianggen, Mao Shuang, Cai Wanfei, Zheng Yan, Liu Liuxie. Theoretical Studies on the Gas-Phase S_NAr Reactions of Halobenzenes and Halide Anions[J]. Chemistry, ;2016, 79(5): 418-424. shu

Theoretical Studies on the Gas-Phase S_NAr Reactions of Halobenzenes and Halide Anions

1.
College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610068

Received Date: 12 August 2015
Available Online: 29 October 2015
Fund Project:

The gas-phase S_NAr reactions of halobenzenes and halide anions (ArY + X^-=ArX + Y^-, X, Y=F, Cl, Br and I) were investigated by the B3LYP and MP2 methods with the 6-311+G** basis set. Calculated results indicate that the S_NAr reactions of halobenzenes and halide anions in the gas-phase proceed via a concerted mechanism, while a two-step addition-elimination pathway is founded with the formation of a stable σ-complex for X=Y=F. In view of thermodynamics and kinetics, the gas-phase S_NAr reactions of halobenzenes attacked by fluoride ion are easy to proceed (overall barrier ΔG^b=9.0~17.3 kJ/mol), whereas it would be hardly possible to observe the reactions for X=Cl^-, Br^- and I^- due to the higher overall barriers (ΔG^b=91.3~202.5 kJ/mol). In addition, the reactivities of the titled reactions can be analyzed by proton affinity (PA), the highest occupied orbital energy (E_HOMO) and Mulliken electronegativity (χ) of the halide as well as the Wiberg bond order (BO) and NPA charges (Q). The break of the C-Y bond in transition state (TS) is mainly responsible for the reaction barriers, and the nucleophilicity of the halide anion is mainly dominated by E_HOMO, while the leaving-group ability of halogen anion is governed by PA or χ.
- S_NAr reaction,
- Nucleophile,
- Reactivity,
- B3LYP,
- Reaction mechanism
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Theoretical Studies on the Gas-Phase SNAr Reactions of Halobenzenes and Halide Anions

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通讯作者: 陈斌, bchen63@163.com

Theoretical Studies on the Gas-Phase S_NAr Reactions of Halobenzenes and Halide Anions