Anisotropies in electronic densities and electrostatic potentials of Halonium Ions: focus on Chlorine, Bromine and Iodine.

Autor: Ramasami P; Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius.; Centre of Natural Product Research, Department of Chemical Sciences, University of Johannesburg, Doornfontein Campus, Johannesburg, 2028, South Africa., Murray JS; Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA. jane.s.murray@gmail.com.
Jazyk: angličtina
Zdroj: Journal of molecular modeling [J Mol Model] 2024 Feb 23; Vol. 30 (3), pp. 81. Date of Electronic Publication: 2024 Feb 23.
DOI: 10.1007/s00894-024-05869-5
Abstrakt: Context: Why are the halonium cations so effective in forming strongly-bound complexes? We directed our research to address this question and we present electrostatic potential data for the valence-state halogen atoms X and halonium cations X + , where X = Cl, Br, I. The electron densities and electrostatic potentials of the halonium cations show considerably greater anisotropy than do the valence state halogens. The distances from the electrostatic potential surface maxima to the halogen nuclei are about 0.5 Å smaller than the distances from the electrostatic potential surface minima to the nuclei, giving the halonium cations each a more disk-like shape than the corresponding neutral valence state halogens. Their surface electrostatic potentials are totally consistent with the directionalities of halonium cations in complexes and the strengths of their interactions. To add perspective to this brief report, we have included calculations of the isotropic cation K + and noble gas Kr.
Methods: The calculations of the electrostatic potentials of the valence states of the halogen atoms Cl, Br and I and the halonium cations Cl + , Br + and I + , as well as K + and Kr, on 0.001 au contours of their electronic densities were carried out with Gaussian O9 and the Wave Function Analysis - Surface Analysis Suite (WFA-SAS) at the M06-2X/6-31 + G(d,p) and M06-2X/3-21G* levels.
(© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)
Databáze: MEDLINE
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