Density Functional Theoretical Studies on Effect of Intramolecular Hydrogen Bonds on Reduction of Nitrophenols

作者：Zhang Hongmei; Liu Yan; Ma Fangping; Qiu Wei; Lei Bo; Shen Jinyou^*; Sun Xiuyun; Han Weiqing; Li Jiansheng; Wang Lianjun^*

来源：Chemical Research in Chinese Universities, 2017, 33(5): 785-793.

DOI：10.1007/s40242-017-7066-1

• Nitrophenol
• Reduction
• Intramolecular hydrogen bond
• Effect mechanism
• Density functional theory

Intramolecular hydrogen bonds(IMHBs) can lead to different physicochemical characteristics of nitrophenols(NPs) that determine their environmental behavior. In the present work, to reveal the relationship between IMHB and nitrophenol reduction, the effects of IMHB on the molecular geometries and properties of a series of nitrophenols were investigated with density functional theory(DFT) calculations. The results of the geometry optimization and atoms-in-molecules(AIM) analysis indicate relatively strong IMHBs in ortho-substituted nitrophenols, whose stability could be significantly improved. In comparing the ELumo and adiabatic electron affmities(AEA) of the nitrophenol isomers, the presence of IMHBs benefited the reductive degradation of NPs, consistent with a previous study. To gain an insight into the effect mechanism of IMHBs on the reductive degradation behavior of these molecules, the condensed electrophilicity Fukui index(f(-)), natural charges and Wiberg bond orders of these nitrophenol isomers were calculated. The calculations indicate that the electrophilic reactivity activity of the O atom on the nitro group could be significantly improved due to the formation of IlVIHBs, which results in the enhanced reductive degradation of ortho-substituted NPs.

• 出版日期2017-10
• 单位中国航天科工集团公司; 南京理工大学