Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements

The interaction between alkaline-earth derivatives with the general formula X2M (X = H, F and Cl; M = Be, Mg and Ca) and a set of Lewis bases, including first and second-row hydrides, namely YHn(Y = O, N, F, S, P and Cl) hydrides, as well as other typical cyclic organic bases, such as aniline, 1H-1,...

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Authors: Montero Campillo, M. Merced, Sanz, Pablo, Mo Romero, Otilia, Yáñez Montero, Manuel, Alkorta, Ibon, Elguero, José
Format: article
Publication Date:2017
Country:España
Institution:Universidad Autónoma de Madrid
Repository:Biblos-e Archivo. Repositorio Institucional de la UAM
Language:English
OAI Identifier:oai:repositorio.uam.es:10486/684710
Online Access:http://hdl.handle.net/10486/684710
https://dx.doi.org/10.1039/C7CP07891A
Access Level:Open access
Keyword:Beryllium bonds
Magnesium bonds
Calcium bonds
Deformation energy
Basicity enhancement
Ab initio calculations
Química
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spelling Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancementsMontero Campillo, M. MercedSanz, PabloMo Romero, OtiliaYáñez Montero, ManuelAlkorta, IbonElguero, JoséBeryllium bondsMagnesium bondsCalcium bondsDeformation energyBasicity enhancementAb initio calculationsQuímicaThe interaction between alkaline-earth derivatives with the general formula X2M (X = H, F and Cl; M = Be, Mg and Ca) and a set of Lewis bases, including first and second-row hydrides, namely YHn(Y = O, N, F, S, P and Cl) hydrides, as well as other typical cyclic organic bases, such as aniline, 1H-1,2,3-triazole, 1H-tetrazole and phenylphosphine, was investigated using the G4 ab initio composite method. Contrary to what was expected, it was found that the interactions involving Mg and Ca derivatives were not necessarily weaker than those between beryllium bonds. The origin is two-fold: larger deformation of the interacting systems when Be-derivatives are involved and appearance of secondary non-covalent interactions in the formation of some of the Mg- and Ca-containing complexes. Hence, the dissociation of the latter complexes may require higher enthalpies than that of the Be complexes. These deformations are triggered by a significant redistribution of electron density of the two interacting moieties, which also result in dramatic changes in the reactivity of the interacting compounds and in particular in the intrinsic basicity of the Lewis bases investigated, to the point that conventional bases, such as ammonia or aniline, upon complexation with MCl2(M = Be, Mg and Ca), become stronger Brønsted acids than phosphoric acid, whereas other bases, such as 1H-tetrazole, become stronger acids than perchloric acid.This work was carried out with financial support from the Ministerio de Economía, Industria y Competitividad (projects CTQ2015-63997-C2 and CTQ2013-43698-P), by the COST Action CM1204 and Comunidad Autónoma de Madrid (S2013/MIT2841, Fotocarbon)Royal Society of ChemistryDepartamento de QuímicaFacultad de CienciasUAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)20172017-12-19research articlehttp://purl.org/coar/resource_type/c_2df8fbb1AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/684710https://dx.doi.org/10.1039/C7CP07891Areponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6847102026-06-23T12:46:27Z
dc.title.none.fl_str_mv Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
title Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
spellingShingle Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
Montero Campillo, M. Merced
Beryllium bonds
Magnesium bonds
Calcium bonds
Deformation energy
Basicity enhancement
Ab initio calculations
Química
title_short Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
title_full Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
title_fullStr Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
title_full_unstemmed Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
title_sort Alkaline-earth (Be, Mg and Ca) bonds at the origin of huge acidity enhancements
dc.creator.none.fl_str_mv Montero Campillo, M. Merced
Sanz, Pablo
Mo Romero, Otilia
Yáñez Montero, Manuel
Alkorta, Ibon
Elguero, José
author Montero Campillo, M. Merced
author_facet Montero Campillo, M. Merced
Sanz, Pablo
Mo Romero, Otilia
Yáñez Montero, Manuel
Alkorta, Ibon
Elguero, José
author_role author
author2 Sanz, Pablo
Mo Romero, Otilia
Yáñez Montero, Manuel
Alkorta, Ibon
Elguero, José
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
UAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)
dc.subject.none.fl_str_mv Beryllium bonds
Magnesium bonds
Calcium bonds
Deformation energy
Basicity enhancement
Ab initio calculations
Química
topic Beryllium bonds
Magnesium bonds
Calcium bonds
Deformation energy
Basicity enhancement
Ab initio calculations
Química
description The interaction between alkaline-earth derivatives with the general formula X2M (X = H, F and Cl; M = Be, Mg and Ca) and a set of Lewis bases, including first and second-row hydrides, namely YHn(Y = O, N, F, S, P and Cl) hydrides, as well as other typical cyclic organic bases, such as aniline, 1H-1,2,3-triazole, 1H-tetrazole and phenylphosphine, was investigated using the G4 ab initio composite method. Contrary to what was expected, it was found that the interactions involving Mg and Ca derivatives were not necessarily weaker than those between beryllium bonds. The origin is two-fold: larger deformation of the interacting systems when Be-derivatives are involved and appearance of secondary non-covalent interactions in the formation of some of the Mg- and Ca-containing complexes. Hence, the dissociation of the latter complexes may require higher enthalpies than that of the Be complexes. These deformations are triggered by a significant redistribution of electron density of the two interacting moieties, which also result in dramatic changes in the reactivity of the interacting compounds and in particular in the intrinsic basicity of the Lewis bases investigated, to the point that conventional bases, such as ammonia or aniline, upon complexation with MCl2(M = Be, Mg and Ca), become stronger Brønsted acids than phosphoric acid, whereas other bases, such as 1H-tetrazole, become stronger acids than perchloric acid.
publishDate 2017
dc.date.none.fl_str_mv 2017
2017-12-19
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/684710
https://dx.doi.org/10.1039/C7CP07891A
url http://hdl.handle.net/10486/684710
https://dx.doi.org/10.1039/C7CP07891A
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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