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Citation: LIU Le-Yan, GENG Zhi-Yuan, ZHAO Cun-Yuan, WANG Yong-Cheng, LI Zhao-Hui. Gas-phase Reaction Mechanism of Allyl anion with N₂O[J]. Acta Physico-Chimica Sinica, ;2007, 23(02): 217-222. doi: 10.3866/PKU.WHXB20070215 shu

Gas-phase Reaction Mechanism of Allyl anion with N₂O

1.
Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China

Received Date: 17 July 2006
Available Online: 30 January 2007

The gas-phase reaction mechanism of allyl anion with N2O was investigated at the MP2/6-31G(d,p) level of the MP2 theory. The single-point energies have also been refined at the CCSD(T)/6-31G(d,p) level to get more accurate energies using the MP2/6-31G(d,p) optimized geometries. The computational results indicated that the reaction involved three reaction pathways to produce cis-vinyl-diazomethyl anion, trans-vinyl-diazomethyl anion, and allenyl anion. The major competition channels of the reaction which produced cis-vinyl-diazomethyl anion, and trans-vinyl-diazomethyl anion all involved two steps of α-H migration. Furthermore, all these rate-determing steps are the second α-H migration and the barriers are 89.79 and 97.93 kJ·mol-1, respectively. Distinctly, allenyl anion was formed through one α-H and one β-H migration and its rate-determing step was the rotation of the N10—O11 and N9—C3 bonds around N—N bond. The rate coefficients of the rate-determining step of all the reaction channels have also been calculated using statistic thermodynamics and conventional transition state theory at 298 K.
- Allyl anion;reaction mechanism;Second-order Moller-Plesset perturbation theory (MP2);Transition state theory
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沈阳化工大学材料科学与工程学院沈阳 110142

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Gas-phase Reaction Mechanism of Allyl anion with N2O

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通讯作者: 陈斌, bchen63@163.com

Gas-phase Reaction Mechanism of Allyl anion with N₂O