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Reaction mechanism of oxidative desulfurization of heterocyclic organic sulfides: a computational study

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Abstract

The potential energy surfaces of the oxidation of two model heterocyclic organic sulfides thiophene and benzothiophene were examined using H2O2 and HCO3H as oxidants adopting CCSD(T), ωB97X-D, M06-2X and B3LYP at the 6-311+G (d,p) level of theory. Stationary points on the potential energy surfaces for the first and second oxidation reaction were fully optimized and characterized. The natural orbital population analysis was also performed to understand the charge distribution. The results suggest that the oxidation of benzothiophene is faster than that of thiophene using both oxidants, and HCO3H is more efficient than H2O2 in oxidation of both sulfides, which are in accordance with the experimental observation. Such results may assist in understanding the reaction mechanism of the oxidative desulfurization of sulfides.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 21173273) and the Dr. Start Fund of Guangdong University of Petrochemical Technology. N.J.D. thanks The University of Memphis High Performance Computing Facility and Computational Research on Materials Institute (CROMIUM) for computing support.

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Authors and Affiliations

  1. College of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming, 525000, People’s Republic of China

    Xingye Zeng, Hanlu Wang, Guidi Mo & Rujin Zhou

  2. Department of Chemistry, The University of Memphis, Memphis, TN, 38152-3550, USA

    Nathan J. DeYonker

  3. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, People’s Republic of China

    Cunyuan Zhao

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  1. Xingye Zeng
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  2. Hanlu Wang
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  3. Nathan J. DeYonker
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  4. Guidi Mo
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  5. Rujin Zhou
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Correspondence to Hanlu Wang.

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Zeng, X., Wang, H., DeYonker, N.J. et al. Reaction mechanism of oxidative desulfurization of heterocyclic organic sulfides: a computational study. Theor Chem Acc 133, 1498 (2014). https://doi.org/10.1007/s00214-014-1498-1

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  • DOI: https://doi.org/10.1007/s00214-014-1498-1

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