Get access

Theoretical study of the mechanism of CH2CO + CN reaction

Authors

  • Hao Sun,

    1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China
    Search for more papers by this author
  • Hong-Qing He,

    1. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Jiefang Road 119, Changchun 130023, People's Republic of China
    Search for more papers by this author
  • Bo Hong,

    1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China
    Search for more papers by this author
  • Ying-Fei Chang,

    1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China
    Search for more papers by this author
  • Zhe An,

    1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China
    Search for more papers by this author
  • Rong-Shun Wang

    Corresponding author
    1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China
    • Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China
    Search for more papers by this author

Abstract

The potential energy surface information of the CH2CO + CN reaction is obtained at the B3LYP/6-311+G(d,p) level. To gain further mechanistic knowledge, higher-level single-point calculations for the stationary points are performed at the QCISD(T)/6-311++G(d,p) level. The CH2CO + CN reaction proceeds through four possible mechanisms: direct hydrogen abstraction, olefinic carbon addition–elimination, carbonyl carbon addition–elimination, and side oxygen addition–elimination. Our calculations demonstrate that R→IM1→TS3→P3: CH2CN + CO is the energetically favorable channel; however, channel R→IM2→TS4→P4: CH2NC + CO is considerably competitive, especially as the temperature increases (R, IM, TS, and P represent reactant, intermediate, transition state, and product, respectively). The present study may be helpful in probing the mechanism of the CH2CO + CN reaction. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006

Ancillary