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Substituent effects on the properties of the hemi-bonded complexes (XH2P···NH2Y)+ (X, Y=H, F, Cl, Br, NH2, CH3, OH)

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Abstract

Ab initio calculations have been performed to study the structures, binding energies, and bonding properties of the hemi-bonded binary complexes (XH2P···NH2Y)+ with the substituents X and Y being H, F, Cl, Br, NH2, CH3, and OH. The P···N interactions in these open-shelled systems have typical pnicogen bond characteristics but much stronger than the usual pnicogen bonds in closed-shell systems. This P···N bond can be strengthened by an electron-withdrawing substituent X or an electron-donating substituent Y, the bonding energy varies from 17 kcal mol-1 of (CH3H2P···NH2F)+ to 54 kcal mol-1 of (FH2P···NH2CH3)+. A nearly linear X-P···N arrangement is required by the pnicogen bond P···N and results in a strong hyperconjugation and charge transfer from the N lone pair to the X-P σ* antibond orbital for α spin, the P···N interaction is described as a single-electron σ bond of β spin. The AIM and NBO analyses revealed that the P···N bonds in the majority of the hemi-bonded complexes are partly covalent in nature.

The P···N interactions in the open-shelled systems (XH2P···NH2Y)+ (X, Y=H, F, Cl, Br, NH2, CH3, OH) with bonding energy of 17~54 kcal mol-1 have typical pnicogen bond characteristics but much stronger than the usual pnicogen bonds in closed-shell systems. This P···N bond can be strengthened by an electron-withdrawing substituent X or an electron-donating substituent Y

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Southwest University, Tiansheng Road No.1, Chongqing, 400715, People’s Republic of China

    Li Fei Ji, An Yong Li & Zhuo Zhe Li

  2. Citrus Research Institute, Southwest University, Tiansheng Road No.1, Chongqing, 400715, People’s Republic of China

    Zhi Xing Ge

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Ji, L.F., Li, A.Y., Li, Z.Z. et al. Substituent effects on the properties of the hemi-bonded complexes (XH2P···NH2Y)+ (X, Y=H, F, Cl, Br, NH2, CH3, OH). J Mol Model 22, 1 (2016). https://doi.org/10.1007/s00894-015-2876-x

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