Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations....

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Main Authors:	Boughlala, Zakaria, Fonseca Guerra, Célia, Bickelhaupt, F. Matthias
Format:	Online
Language:	English
Published:	John Wiley and Sons Inc. 2016
Online Access:	https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4984409/

id	pubmed-4984409
recordtype	oai_dc
spelling	pubmed-49844092016-08-22 Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism Boughlala, Zakaria Fonseca Guerra, Célia Bickelhaupt, F. Matthias Full Papers We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. John Wiley and Sons Inc. 2016-02-22 /pmc/articles/PMC4984409/ /pubmed/27551660 http://dx.doi.org/10.1002/open.201500208 Text en © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial (http://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
repository_type	Open Access Journal
institution_category	Foreign Institution
institution	US National Center for Biotechnology Information
building	NCBI PubMed
collection	Online Access
language	English
format	Online
author	Boughlala, Zakaria Fonseca Guerra, Célia Bickelhaupt, F. Matthias
spellingShingle	Boughlala, Zakaria Fonseca Guerra, Célia Bickelhaupt, F. Matthias Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism
author_facet	Boughlala, Zakaria Fonseca Guerra, Célia Bickelhaupt, F. Matthias
author_sort	Boughlala, Zakaria
title	Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism
title_short	Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism
title_full	Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism
title_fullStr	Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism
title_full_unstemmed	Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism
title_sort	alkali metal cation versus proton and methyl cation affinities: structure and bonding mechanism
description	We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.
publisher	John Wiley and Sons Inc.
publishDate	2016
url	https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4984409/
_version_	1613627282021154816

Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

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