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Aromaticity of azines through dyotropic double hydrogen transfer reaction

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Abstract

Density functional theory calculations have been performed at B3LYP/6–31+G (d) level to quantify the aromaticities of mono- to triazines through dyotropic double hydrogen transfer (DDHT) reaction. The reaction was chosen such that the azines are products of double hydrogen dyotropic rearrangement, and activation barriers and energies of the reactions were functions of the aromaticities of azines. Small activation barriers and high energies of reactions were characteristic of the reactions delivering highly aromatic azines. Synchronicity, reaction energies and energies of activation have been analyzed, and the aromaticity values obtained thereof were compared with the aromaticity values from other geometric and magnetic criteria. Energies of activation were found superior to the energies of reaction for the determination of the aromaticities. Aromaticities of most of the azines were comparable to the aromaticity of benzene. Activation barriers and reaction energies for the dyotropic reactions delivering contiguous or polynitrogeneous azines had thermodynamic contributions arising from the contiguous nature of azines, in addition to the aromaticity related thermodynamic contributions. Moreover, the aromaticity values of azines are also affected by the fusion of azine to the reaction center. When corrected for these factors, the aromaticities of azines using energies of activation for DDHT correlated nicely with the aromaticities of azines reported in the literature through NICS (0) πzz and some other energetic methods.

Azines have aromaticities comparable to benzene.

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Acknowledgments

K.A. acknowledges the Higher Education Commission (HEC) of Pakistan (Grant No.20-1899/R & D/10/8863-), COMSATS Institute of Information Technology and King Faisal University for financial support to the project. R.L acknowledges the support to this work by the project “Light2Hydrogen” of the BMBF and the project “Nano4Hydrogen” of the ESF and the state of Mecklenburg-Vorpommern.

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Authors and Affiliations

  1. COMSATS Institute of Information Technology, Abbottabad, KPK, Pakistan, 22060

    Maria, Muhammad Hanif, Tariq Mahmood & Khurshid Ayub

  2. Department of Physical Chemistry, University of Rostock, Dr.-Lorenz-Weg 1, 18059, Rostock, Germany

    Ralf Ludwig

  3. Leibniz-Institut für Katalyse an der Universität Rostock, e. V. Alebert-Einstein-Strasse 29a, 18059, Rostock, Germany

    Ralf Ludwig

  4. Department of Chemistry, College of Science, King Faisal University, Al-Ahsa, 31982, Kingdom of Saudi Arabia

    Khurshid Ayub

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  1. Maria
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  2. Muhammad Hanif
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  3. Tariq Mahmood
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  5. Khurshid Ayub
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Correspondence to Khurshid Ayub.

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Maria, Hanif, M., Mahmood, T. et al. Aromaticity of azines through dyotropic double hydrogen transfer reaction. J Mol Model 20, 2304 (2014). https://doi.org/10.1007/s00894-014-2304-7

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