Halogen bonding with the halogenabenzene bird structure, halobenzene and halocyclopentadiene
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The ability of the “bird-like” halogenabenzene molecule, referred to as X-bird (X= Cl to At), to form halogen-bonded complexes with the nucleophiles H2O and NH3 was investigated using double-hybrid density functional theory and the aug-cc-pVTZ/aug-cc-pVTZ-PP basis set. The structures and interaction energies were compared with 5-halocyclopenta-1,3-diene (halocyclopentadiene; an isomer of halogenabenzene) and halobenzene, also complexed with H2O and NH3. The unusual structure of the X-bird, with the halogen bonded to two carbon atoms, results in two distinct σ-holes, roughly at the extension of the C-X bonds. Based on the behaviour of the interaction energy (which increases for heavier halogens) and van der Waals (vdW) ratio (which decreases for heavier halogens), it is concluded that the X-bird forms proper halogen bonds with H2O and NH3. The interaction energies are larger than those of the halogen-bonded complexes involving halobenzene and halocyclopentadiene, presumably due to the presence of a secondary interaction.
Cates , E L & van Mourik , T 2019 , ' Halogen bonding with the halogenabenzene bird structure, halobenzene and halocyclopentadiene ' , Journal of Computational Chemistry , vol. 40 , no. 24 , pp. 2111-2118 . https://doi.org/10.1002/jcc.25863
Journal of Computational Chemistry
Copyright © 2019 Wiley Periodicals, Inc. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/jcc.25863
DescriptionWe thank EastCHEM for support via the EaStCHEM Research Computing Facility. The research data supporting this publication cab be accessed at https://doi.org/10.17630/a3b1f172-dd54-4df1-a498-9951cfce9cee.
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