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Theoretical Study on the Correlation of the Experimental Nucleophilic and Electrophilic Reaction Rates of Aromatic Compounds with the Prediction Results of Theoretical Methods
Received date: 2016-02-26
Revised date: 2016-05-12
Online published: 2016-06-01
Supported by
Project supported by the National Natural Science Foundation of China (Nos.21173020, 21473008).
Natural population analysis (NPA) charge, Hirshfeld charge, electrostatic potential, average local ionization energy, orbital composition of lowest unoccupied molecular orbital (LUMO), condensed Fukui function and condensed dual descriptor were exploited to predict the reaction active sites of nucleophilic and electrophilic reactions of aromatic compounds. It was found that the predicted reaction sites of these methods were all in consistent with the experimental results. It was also found that the correlations of the prediction results of theoretical methods reflecting local hardness such as Hirshfeld charges and electrostatic potential with the experimental reaction rate were excellent no matter the reactions of aromatic compounds are nucleophilic or electrophilic. However, the prediction results of theoretical methods reflecting local softness such as the condensed Fukui function and the condensed dual descriptor were in poor correlation with the experimental reaction rates as unexpected.
Cao Jingsi , Chen Feiwu . Theoretical Study on the Correlation of the Experimental Nucleophilic and Electrophilic Reaction Rates of Aromatic Compounds with the Prediction Results of Theoretical Methods[J]. Chinese Journal of Organic Chemistry, 2016 , 36(10) : 2463 -2471 . DOI: 10.6023/cjoc201602026
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