GAS-PHASE REACTION OF THE ISOBUTENYL ANION WITH N2O FROM AB INITIO CALCULATIONS
J.X. Liang1, Y.B. Wang1, Z.Y. Geng2,3, Y.Z. Wang2,3, Y.C. Wang2,3
1College of Chemical Engineering, Northwest University for Nationalities, Lanzhou, Gansu, P. R. China
wangyb16@yahoo.cn
2Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Key Laboratory of Eco-environment-related Polymer Materials
3Ministry of Education, Northwest Normal University, Lanzhou, Gansu, P. R. China
Keywords: isobutenyl anion, reaction mechanism, second-order Moller—Plesset perturbation theory (MP2)
Abstract
Calculations using conventional ab initio theory are performed to investigate the reaction mechanism associated with the gas-phase ion/molecule reaction of isobutenyl anion with N2O. As a result, our theoretical findings strongly suggest that the main pathway is the reaction pattern of end-N attack and that the corresponding reaction mechanism basically relates to hydrogen migration, which may yield products cis-CH2(CH3)CCN–2, trans-CH2(CH3)CCN–2, and H2O. Those are in good agreement with the experimental observations. Moreover, based on the NBO, Activation Strain model and methyl group effect analysis, we also explored the characters of rate-determining step of the main pathway.
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