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

Li, Ping, Wang, Weihua, Sun, Qiao, Li, Zhen, Du, Aijun, Bi, Siwei and Zhao, Yan (2013) 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. ChemPhysChem, 14 12: 2737-2743. doi:10.1002/cphc.201300395


Author Li, Ping
Wang, Weihua
Sun, Qiao
Li, Zhen
Du, Aijun
Bi, Siwei
Zhao, Yan
Title 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
Journal name ChemPhysChem   Check publisher's open access policy
ISSN 1439-4235
1439-7641
Publication date 2013-08-01
Sub-type Article (original research)
DOI 10.1002/cphc.201300395
Volume 14
Issue 12
Start page 2737
End page 2743
Total pages 7
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag
Collection year 2014
Language eng
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-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.
Keyword Density functional calculations
Hydrogen peroxide
Radicals
Reaction mechanisms
Water chemistry
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
Australian Institute for Bioengineering and Nanotechnology Publications
 
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