Superalkali Li₃M (M = Cl, Br, I) as a Lewis base in halogen bonding: A heavier halogen is a stronger Lewis base than a lighter halogen

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• 作者：WenKai Tian ; Qin Miao ; QingZhong Li ; ^{liqingzhong1990@sina.com} ; WenZuo Li ; JianBo Cheng
• 关键词：Halogen bond ; Superatom ; Orbital interaction ; Li3Cl ; Li3Br
• 刊名：Computational and Theoretical Chemistry
• 出版年：2013
• 出版时间：15 May, 2013
• 年：2013
• 卷：1012
• 期：Complete
• 页码：41-46
• 全文大小：456 K

文摘

The Li₃M-XY (M = Cl, Br, and I; XY = ClCl, BrBr, ClF, BrCl, and BrF) complexes have been studied with theoretical calculations at the MP2/aug-cc-pVTZ level. The results showed that the Br atom in Li₃Br is a stronger halogen acceptor than the Cl atom in Li₃Cl when it interacts with dihalogen molecules although their strength difference is small and the Li₃I is the strongest Lewis base. To the best of our knowledge, this is the first report on halogen bonds involved with superatoms. The formation of halogen bonding has been analyzed with natural bond orbital (NBO), atoms in molecules (AIM), and energy decomposition. The results showed that the orbital interaction plays an important role for the stabilization of the complexes, which is different from conventional halogen bonds.