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Vol. 27 No. 8 (2015): Vol 27 Issue 8

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Theoretical and Computational Study of Tautomerization of Ketenimine to Acetonitrile

https://doi.org/10.14233/ajchem.2015.18907
O.I. Osman
Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589,Saudi Arabia; Chemistry Department, Faculty of Science, University of Khartoum, P.O. Box 321, Khartoum 11111,Sudan

Corresponding Author(s) : O.I. Osman

oabdelkarim@kau.edu.sa

Asian Journal of Chemistry, Vol. 27 No. 8 (2015): Vol 27 Issue 8

Abstract

 ab initio electronic structure computations employing MP2, DFT(B3LYP) and CCSD methods with


6-311++G**, aug-cc-pvdz and aug-cc-pvtz basis sets have been performed for the equilibrium
geometries and transition state involved in the interconversion between ketenimine (I) and acetonitrile
(II). A direct unimolecular 1,3-hydrogen shift pathway for the ketenimine  acetonitrile rearrangement
was proposed. The activation energies of this mechanistic route range between 57.066 and 71.489
kcal/mol. They are in excellent agreement with the reported experimental value. The proposed
tautomerization route was also supported by thermodynamic and natural bond orbital analyses.

Keywords

 Ketenimine Acetonitrile Tautomerization Activation energy Hyperconjugation
Osman, . O. (2015). Theoretical and Computational Study of Tautomerization of Ketenimine to Acetonitrile. Asian Journal of Chemistry, 27(8), 3091–3096. https://doi.org/10.14233/ajchem.2015.18907
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