Theoretical and Computational Study of Tautomerization of Ketenimine to Acetonitrile

摘要

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 me 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.