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Theoretical study of X- · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2): noncovalently electron-withdrawing effects on anion-arene interactions

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Abstract

The ternary complexes X- · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2) have been investigated by MP2 calculations to understand the noncovalently electron-withdrawing effects on anion-arene interactions. The results indicate that in binary complexes (1 · X-), both weak σ-type and anion-π complexes can be formed for Cl- and Br-, but only anion-π complex can be formed for I-. Moreover, the hydrogen-bonding complex is the global minimum for all three halides in binary complexes. However, in ternary complexes, anion-π complex become unstable and only σ complex can retain in many cases for Cl- and Br-. Anion-π complex keeps stable only when YF = HF. In contrast with binary complexes, σ complex become the global minimum for Cl- and Br- in ternary complexes. These changes in binding mode and strength are consistent with the results of covalently electron-withdrawing effects. However, in contrast with the covalently electron-withdrawing substituents, Cl- and Br- can attack the aromatic carbon atom to form a strong σ complex when the noncovalently electron-withdrawing effect is induced by halogen bonding. The binding behavior for I- is different from that for Cl- and Br- in two aspects. First, the anion-π complex for I- can also keep stable when the noncovalent interaction is halogen bonding. Second, the anion-π complex for I- is the global minimum when it can retain as a stable structure.

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Acknowledgments

Supported by the High Performance Computing Center, Kunming Institute of Botany, CAS, China.

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  1. School of Chemistry & Chemical Engineering, Qujing Normal University, Qujing, 655011, Yunnan, China

    Yishan Chen & Lifeng Yao

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  1. Yishan Chen
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Correspondence to Yishan Chen.

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Chen, Y., Yao, L. Theoretical study of X- · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2): noncovalently electron-withdrawing effects on anion-arene interactions. J Mol Model 20, 2076 (2014). https://doi.org/10.1007/s00894-014-2076-0

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  • DOI: https://doi.org/10.1007/s00894-014-2076-0

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