Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (11): 2055-2062.doi: 10.3866/PKU.WHXB201409193

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Hirshfeld Charge as a Quantitative Measure of Electrophilicity and Nucleophilicity: Nitrogen-Containing Systems

ZHOU Xia-Yu1, RONG Chun-Ying2, LU Tian3, LIU Shu-Bin4   

  1. 1. Department of Pharmacy, Changde Vocational Technical College, Changde 415000, Hunan Province, P. R. China;
    2. Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research Ministry of Education of China and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. China;
    3. Beijing Kein Research Center for Natural Sciences, Beijing 100022, P. R. China;
    4. Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, U.S.A.
  • Received:2014-08-07 Revised:2014-09-19 Published:2014-10-30
  • Contact: RONG Chun-Ying, LIU Shu-Bin E-mail:rongchunying@aliyun.com;shubin@email.unc.edu
  • Supported by:

    The project was supported by the Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, China (Xiang Tong Jiao [2012]318), Hunan Provincial Natural Science Foundation, China (12JJ2029), Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, China (12K030), Scientific Research Fund of Changde Municipal Science and Technology Bureau, Hunan Province, China (2014JF15), and Provincial Science and Technology Project, China (2013FJ4220).

Abstract:

To accurately predict the capability and possible reaction site for atoms in molecules to donate or accept electrons in chemical processes, i.e., to quantitatively determine electrophilicity, nucleophilicity, and regioselectivity, is an important yet incomplete task. Earlier, we proposed using the Hirshfeld charge and information gain as two equivalent descriptors for this purpose, based on the Information Conservation Principle we recently proposed. This idea was successfully applied to two series of molecular systems to confirm its validity. However, our previous work is hindered by the fact that the involved element is carbon. It is unclear if stockit applies to other elements and to different valence states of the same element. In this study, to address these issues, the method was applied to nitrogen-containing systems. Five different categories of compounds were studied, including benzenediazonium, azodicarboxylate, diazo, and primary and secondary amines, with a total of 40 molecules. The results show that there are strong linear correlations between the Hirshfeld charge and their experimental scales of electrophilicity and nucleophilicity. However, these correlations depend on the valence state and bonding environment of the nitrogen element. The linear relationship only holds within the same category. Possible reasons for this observation are discussed.

Key words: Hirshfeld charge, Information gain, Electrophilicity, Nucleophilicity, Regioselectivity

MSC2000: 

  • O641