Understanding the effect of substitution on the formation of S. . .F chalcogen bond

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• 作者：RAHUL SHUKLA ; DEEPAK CHOPRA
• 关键词：Non ; covalent interactions ; chalcogen bonds ; binding energies ; energy decomposition ; topology ; NBO
• 刊名：Journal of Chemical Sciences
• 出版年：2016
• 出版时间：October 2016
• 年：2016
• 卷：128
• 期：10
• 页码：1589-1596
• 全文大小：2,056 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Chemistry
  
• 出版者：Springer India
• ISSN：0973-7103
• 卷排序：128

文摘

In this study, we have investigated the effect of substitution on the formation of S …F non-covalent interactions in XHS …FCH₃ complexes (X =-H, -F, -Cl, -OH, -OCH₃, -NH₂, -NHCH₃, -NO₂, -CN) at MP2/aug-cc-pVDZ level of theory. The formation of S …F chalcogen bonds was observed in all the cases, except for X = -H. The binding energy of the S …F non-covalent interactions is strongly dependent on the nature of the substituent groups. The energy decomposition analysis revealed that electrostatic and exchange energy component are the dominant contributors towards the stability of these interactions. The topological analysis established the presence of the S …F chalcogen bond due to the presence of a bond critical point exclusively between sulphur and fluorine atoms representing a closed-shell interaction. The natural bond orbital analysis shows that the stability of the interaction comes from a charge transfer from F(lp) to s*(S-X) orbital transition.