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A DFT study on the reaction mechanism between tetrachloro-o-benzoquinone and H2O2 and an alternative reaction approach to produce the hydroxyl radical

机译：DFT研究四氯- o -苯醌与H 2 O 2 之间的反应机理以及产生羟基自由基的替代反应方法

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The formation of hydroxyl and alkoxyl radicals in the reaction of halogenated quinones and organic hydroperoxides can be used to elucidate the potential carcinogenicity of polyhalogenated aromatic environmental pollutants. To further enrich the understanding of the reactivity of the halogenated quinones with organic hydroperoxides, in this study, the reaction mechanism of tetrachloro-o-benzoquinone (o-TCBQ) with H2O2 has been systematically investigated at the B3LYP/6-311++G** level. It was found that a molecular complex was formed as the first step of the title reaction. After that, the nucleophilic attack of H2O2 on o-TCBQ occurs to produce an unstable intermediate containing an O–O bond. Subsequently, the unstable intermediate decomposes homolytically via the cleavage of the O–O bond, resulting in the formation of the OH radical. Note that explicit water molecules play an important positive role in the nucleophilic attack process. The nucleophilic attack process is the rate-determining step in the whole reaction. Moreover, selected substitution effects on the title reaction have also been studied. In addition, as an alternative reaction approach, it was found that the formed unstable intermediate containing an O–O bond mentioned above can be produced directly from the nucleophilic attack of the anionic form of H2O2 on o-TCBQ in the absence of explicit water molecules.
机译：卤代醌与有机氢过氧化物的反应中羟基和烷氧基自由基的形成可用于阐明多卤代芳族环境污染物的潜在致癌性。为了进一步丰富对卤代醌与有机氢过氧化物反应性的理解，本研究中四氯- o -苯醌（ o -TCBQ）与H的反应机理已在B3LYP / 6-311 ++ G **级别上系统地研究了 2 O 2 。已经发现，形成分子复合物作为标题反应的第一步。之后，H 2 O 2 对 o -TCBQ的亲核攻击会产生含有O-O键的不稳定中间体。随后，不稳定的中间体通过O–O键的裂解均匀地分解，导致OH自由基的形成。请注意，显性水分子在亲核攻击过程中起着重要的积极作用。亲核攻击过程是整个反应中决定速率的步骤。此外，还研究了对标题反应的选择取代作用。另外，作为一种替代的反应方法，发现形成的含有上述O-O键的不稳定中间体可以直接由阴离子H 2 的亲核攻击产生在没有明确水分子的情况下，在 o -TCBQ上使用 O 2 。

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