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Issue 7, 2018
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Aerogen bonds formed between AeOF2 (Ae = Kr, Xe) and diazines: comparisons between σ-hole and π-hole complexes

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Abstract

The interaction between KrOF2 or XeOF2 and the 1,2, 1,3, and 1,4 diazines is characterized chiefly by a Kr/Xe⋯N aerogen bond, as deduced from ab initio calculations. The most stable dimers take advantage of the σ-hole on the aerogen atom, wherein the two molecules lie in the same plane. The interaction is quite strong, as much as 18 kcal mol−1. A second class of dimer geometry utilizes the π-hole above the aerogen atom in an approximate perpendicular arrangement of the two monomers; these structures are not as strongly bound: 6–8 kcal mol−1. Both sorts of dimers contain auxiliary CH⋯F H-bonds which contribute to their stability, but even with their removal, the aerogen bond energy remains as high as 14 kcal mol−1. The nature and strength of each specific interaction is confirmed and quantified by AIM, NCI, NBO, and electron density shift patterns. There is not a great deal of sensitivity to the identity of either the aerogen atom or the position of the two N atoms in the diazine.

Graphical abstract: Aerogen bonds formed between AeOF2 (Ae = Kr, Xe) and diazines: comparisons between σ-hole and π-hole complexes

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Publication details

The article was received on 30 Nov 2017, accepted on 10 Jan 2018 and first published on 10 Jan 2018


Article type: Paper
DOI: 10.1039/C7CP08048D
Citation: Phys. Chem. Chem. Phys., 2018,20, 4676-4687
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    Aerogen bonds formed between AeOF2 (Ae = Kr, Xe) and diazines: comparisons between σ-hole and π-hole complexes

    W. Zierkiewicz, M. Michalczyk and S. Scheiner, Phys. Chem. Chem. Phys., 2018, 20, 4676
    DOI: 10.1039/C7CP08048D

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