Next Article in Journal
Molecular Theranostic Agents for Photodynamic Therapy (PDT) and Magnetic Resonance Imaging (MRI)
Next Article in Special Issue
Stabilization of Supramolecular Networks of Polyiodides with Protonated Small Tetra-azacyclophanes
Previous Article in Journal
Survey of the Geometric and Electronic Structures of the Key Hydrogenated Forms of FeMo-co, the Active Site of the Enzyme Nitrogenase: Principles of the Mechanistically Significant Coordination Chemistry
Previous Article in Special Issue
Solvent and Substituent Effects on the Phosphine + CO2 Reaction
Open AccessArticle

Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases

Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), Spain
*
Author to whom correspondence should be addressed.
Inorganics 2019, 7(1), 9; https://doi.org/10.3390/inorganics7010009
Received: 31 December 2018 / Revised: 14 January 2019 / Accepted: 15 January 2019 / Published: 17 January 2019
(This article belongs to the Special Issue Novel Non-Covalent Interactions)
We have theoretically studied the formation of hydrogen-bonded (HB) and halogen-bonded (XB) complexes of halogen oxoacids (HXOn) with Lewis bases (NH3 and Cl) at the CCSD(T)/CBS//RIMP2/aug-cc-pVTZ level of theory. Minima structures have been found for all HB and XB systems. Proton transfer is generally observed in complexes with three or four oxygen atoms, namely, HXO4:NH3, HClO3:Cl, HBrO3:Cl, and HXO4:Cl. All XB complexes fall into the category of halogen-shared complexes, except for HClO4:NH3 and HClO4:Cl, which are traditional ones. The interaction energies generally increase with the number of O atoms. Comparison of the energetics of the complexes indicates that the only XB complexes that are more favored than those of HB are HIO:NH3, HIO:Cl, HIO2:Cl, and HIO3:Cl. The atoms-in-molecules (AIM) theory is used to analyze the complexes and results in good correlations between electron density and its Laplacian values with intermolecular equilibrium distances. The natural bon orbital (NBO) is used to analyze the complexes in terms of charge-transfer energy contributions, which usually increase as the number of O atoms increases. The nature of the interactions has been analyzed using the symmetry-adapted perturbation theory (SAPT) method. The results indicate that the most important energy contribution comes from electrostatics, followed by induction. View Full-Text
Keywords: hydrogen bond; halogen bond; ab initio; halogen oxoacids hydrogen bond; halogen bond; ab initio; halogen oxoacids
Show Figures

Graphical abstract

MDPI and ACS Style

Quiñonero, D.; Frontera, A. Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases. Inorganics 2019, 7, 9.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Back to TopTop