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A reinvestigation of the deceptively simple reaction of toluene with OH, and the fate of the benzyl radical: a combined thermodynamic and kinetic study on the competition between OH-addition and H-abstraction reactions

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Abstract

This work reports density functional and composite model chemistry calculations performed on the reactions of toluene with the hydroxyl radical. Both the experimentally observed H-abstraction from the methyl group and possible OH-additions to the phenyl ring were investigated. Reaction enthalpies and barrier heights suggest that H-abstraction is more favorable than OH-addition to the ring. The calculated reaction rates at room temperature and the radical-intermediate product fractions support this view. At first sight, this might seem to disagree with the fact that, under most experimental conditions, cresols are observed in a larger concentration than benzaldehyde. Since the accepted mechanism for benzaldehyde formation involves H-abstraction, a contradiction arises that calls for a more elaborate explanation. In this first exploratory study, we provide evidence that support the preference of H-abstraction over OH-addition and present an alternative mechanism which shows that cresols can be actually produced also through H-abstraction and not only from OH-addition, thus justifying the larger proportion of cresols than benzaldehyde among the products.

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Acknowledgements

This work has been supported by the Italian MIUR (PRIN 2017, project “Physico-chemical Heuristic Approaches: Nanoscale Theory Of Molecular Spectroscopy, PHANTOMS”, prot. 2017A4XRCA). The SMART@SNS Laboratory (http://smart.sns.it) is acknowledged for providing high-performance computer facilities. We gratefully acknowledge the financial contribution for making this study provided by Pedeciba, CSIC (UdelaR) and ANII. Some of the calculations reported in this paper were performed in ClusterUY, a newly installed platform for high-performance scientific computing at the National Supercomputing Center, Uruguay.

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Authors and Affiliations

  1. SMART Lab, Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126, Pisa, Italy

    Zoi Salta & Vincenzo Barone

  2. Physical Chemistry Sector, Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece

    Agnie M. Kosmas

  3. Computational Chemistry and Biology Group, Facultad de Química, CCBG – DETEMA, UdelaR, CC1157, Montevideo, 11000, Uruguay

    Marc E. Segovia, Martina Kieninger & Oscar N. Ventura

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  1. Zoi Salta
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  2. Agnie M. Kosmas
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  4. Martina Kieninger
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  5. Oscar N. Ventura
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  6. Vincenzo Barone
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Correspondence to Zoi Salta, Oscar N. Ventura or Vincenzo Barone.

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Salta, Z., Kosmas, A.M., Segovia, M.E. et al. A reinvestigation of the deceptively simple reaction of toluene with OH, and the fate of the benzyl radical: a combined thermodynamic and kinetic study on the competition between OH-addition and H-abstraction reactions. Theor Chem Acc 139, 112 (2020). https://doi.org/10.1007/s00214-020-02626-8

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