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Insights into the Mechanism of the Reaction between Tetrachloro-p-Benzoquinone and Hydrogen Peroxide and their Implications in the Catalytic Role of Water Molecules in Producing the Hydroxyl Radial

Authors

  • Prof. Dr. Ping Li,

    Corresponding author
    1. Key Laboratory of Life-Organic Analysis, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165 (P. R. China)
    • Key Laboratory of Life-Organic Analysis, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165 (P. R. China)
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  • Dr. Weihua Wang,

    1. Key Laboratory of Life-Organic Analysis, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165 (P. R. China)
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  • Dr. Qiao Sun,

    1. Australian Institute for Bioengineering and Nanotechnology, University of Queensland, QLD 4072 (Australia)
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  • Dr. Zhen Li,

    1. Institute of Superconducting and Electronic Materials, University of Wollongong, NSW 2500 (Australia)
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  • Dr. Aijun Du,

    1. School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, QLD 4001 (Australia)
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  • Prof. Dr. Siwei Bi,

    1. Key Laboratory of Life-Organic Analysis, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165 (P. R. China)
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  • Dr. Yan Zhao

    1. Key Laboratory of Life-Organic Analysis, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165 (P. R. China)
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Abstract

Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O[BOND]O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied.

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