Citation: ZHOU Xia-Yu, RONG Chun-Ying, LU Tian, LIU Shu-Bin. Hirshfeld Charge as a Quantitative Measure of Electrophilicity and Nucleophilicity: Nitrogen-Containing Systems[J]. Acta Physico-Chimica Sinica, ;2014, 30(11): 2055-2062. doi: 10.3866/PKU.WHXB201409193 shu

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

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 Date: 7 August 2014
Available Online: 19 September 2014
Fund Project: 湖南省高校科技创新团队支持计划(湘教通[2012]318 号) (湘教通[2012]318 号) 湖南省自然科学基金(12JJ2029) (12JJ2029) 湖南省高校创新平台开放基金(12K030) (12K030) 常德市科技局重点项目(2014JF15) (2014JF15)湖南省省级科技计划项目(2013FJ4220)资助 (2013FJ4220)

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 cate ries 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 cate ry. Possible reasons for this observation are discussed.
- Hirshfeld charge,
- Information gain,
- Electrophilicity,
- Nucleophilicity,
- Regioselectivity
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