文献类型：期刊文献

英文题名：Pnictogen, chalcogen, and halogen bonds in catalytic systems: theoretical study and detailed comparison

作者：Lu, Ling[1,2];Lu, Yunxiang[1,2];Zhu, Zhengdan[3];Liu, Honglai[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Dept Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, CAS Key Lab Receptor Res, Shanghai 201203, Peoples R China

年份：2020

卷号：26

期号：1

外文期刊名：JOURNAL OF MOLECULAR MODELING

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000511338700003)】；

基金：This work was supported by the National Natural Science Foundation of China (21,473,054 and 91,834,301).

语种：英文

外文关键词：sigma-Hole interactions; Catalysis; Comparison; Binding strength; Activity

摘要：Although halogen bond (XB), a typical sigma-hole noncovalent interaction, has been widely exploited in organocatalysis within the last two decades, only very recently has its sister sigma-hole interactions, such as chalcogen bond (ChB) and pnictogen bond (PnB), begun to be explored for potential applications in catalysis. Herein, a detailed comparison investigation of PnB, ChB, and XB interactions in catalytic systems was performed from a theoretical point of view. Owing to the excellent properties of the pentafluorophenyl moiety (C6F5) in catalysis, the complexes of (C6F5)(3)Pn, (C6F5)(2)Ch, and C6F5X with chloride ion were firstly studied. Then, we successively substituted C6F5 by phenyl groups, to examine the influence of substituents on the characteristics of such interactions. In addition, several halogen-bonded complexes between the donor 1,3,5-trifluoro-2,4,6-triiodobenzene (C6F3I3) and heavier Pn and Ch species as acceptors were also investigated. Our calculations showed that the interactions become gradually stronger upon going from row 3 to 5 and from main group VII to V, which correlates well with the experimental observations. As the strength of the interactions enhances, the contribution of electrostatics to the attraction increases, while the orbital term contribution becomes smaller. Particularly, the significant differences between the three types of sigma-hole interactions found in catalysis and anion transport were clarified.