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On the properties of Se ⋯N interaction: the analysis of substituent effects by energy decomposition and orbital interaction

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Abstract

The nature and strength of intermolecular Se ⋯N interaction between selenium-containing compounds HSeX (X = CH3, NH2, CF3, OCH3, CN, OH, NO2, Cl, F), and NH3 have been investigated at the MP2/aug-cc-pVDZ level. The Se ⋯N interaction is found to be dependent on the substituent groups, which greatly affect the positive electrostatic potential of Se atoms and the accepting electron ability of X-Se σ ∗ antibonding orbital. Energy decomposition of the Se ⋯N interaction reveals that electrostatic and induction forces are comparable in the weak-bonded complexes and induction becomes more significant in the complexes with strong electron-withdrawing substituents. Natural bond orbital (NBO) analysis indicates that the primary source of the induction is the electron transfer from the N lone pair to the X-Se σ ∗ antibonding orbital. The geometry of the complex and the interaction directionality of NH3 to X-Se bond can be regarded as a consequence of the exchange-repulsion. The topological analysis on the electron density reveals the nature of closed-shell interaction in these X-Se ⋯N contacts. The Se ⋯N interaction in the complexes with the strong electron-withdrawing substituent has a partly covalent character.

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Acknowledgments

We are grateful for the financial support from the National Nature Science Foundation of China (grant nos. 21073077 and 21173101).

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  1. State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, Jilin University, Changchun, 130012, People’s Republic of China

    Fangfang Zhou, Ruirui Liu, Jia Tang, Ping Li, Yahui Cui & Houyu Zhang

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  1. Fangfang Zhou
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Zhou, F., Liu, R., Tang, J. et al. On the properties of Se ⋯N interaction: the analysis of substituent effects by energy decomposition and orbital interaction. J Mol Model 22, 29 (2016). https://doi.org/10.1007/s00894-015-2901-0

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