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Resonance bonding in XNgY (X = F, Cl, Br, I; Ng = Kr or Xe; Y = CN or NC) molecules: an NBO/NRT investigation

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Abstract

Several noble-gas-containing molecules XNgY were observed experimentally. However, the bonding in such systems is still not understood. Using natural bond orbital and natural resonance theory (NBO/NRT) methods, the present work investigated bonding of the title molecules. The results show that each of the studied XNgY molecules should be better described as a resonance hybrid of ω-bonding and \( \widehat{\sigma} \)-type long-bonding structures: X:− Ng+ − Y, X − Ng+: Y−, and X^Y. The ω-bonding and long-bonding make competing contributions to the composite resonance hybrid due to the accurately preserved bond order conservation principle. We find that the resonance bonding is highly tunable for these noble-gas-containing molecules due to its dependence on the nature of the halogen X or the central noble-gas atoms Ng. When the molecule XNgY consists of a relatively lighter Ng atom, a relatively low-electronegative X atom, and the CN fragment rather than NC, the long-bonding structure X^Y tends to be highlighted. In contrast, the heavy Ng atom and high-electronegative X atom will enhance the ω-bonding structure. Overall, the present work provides electronic principles and chemical insights that help understand the bonding in these XNgY species.

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Acknowledgments

This work was supported by the Natural Science Foundation of Shandong Province (No. ZR2015BM025). We thank Professor Frank Weinhold of the University of Wisconsin-Madison for his continuous help.

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  1. College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Wenhua East Road 88, Jinan, Shandong, 250014, People’s Republic of China

    Junjie Song, Yue Su, Yanping Jia, Lusheng Chen & Guiqiu Zhang

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  1. Junjie Song
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  2. Yue Su
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Correspondence to Guiqiu Zhang.

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Song, J., Su, Y., Jia, Y. et al. Resonance bonding in XNgY (X = F, Cl, Br, I; Ng = Kr or Xe; Y = CN or NC) molecules: an NBO/NRT investigation. J Mol Model 24, 129 (2018). https://doi.org/10.1007/s00894-018-3665-0

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