Journal
ACTA PHYSICO-CHIMICA SINICA
Volume 30, Issue 11, Pages 2055-2062Publisher
PEKING UNIV PRESS
DOI: 10.3866/PKU.WHXB201409193
Keywords
Hirshfeld charge; Information gain; Electrophilicity; Nucleophilicity; Regioselectivity
Categories
Funding
- 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 [12112029]
- 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]
- Provincial Science and Technology Project, China [2013FJ4220]
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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 it 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.
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