Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)

Equilibrium hydrogen-bond dissociation energies De for the process B HX = B + HX are calculated at the CCSD(T)(F12c)/cc-pVDZ-F12 level for B190 complexes B HX. As established earlier, De values for such complexes can be described by the equation De = cNBEA , in which NB and EHX are the nucleophilici...

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Autores: Alkorta, Ibon, Legon, Anthony
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/282261
Acceso en línea:http://hdl.handle.net/10261/282261
Access Level:acceso abierto
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spelling Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)Alkorta, IbonLegon, AnthonyEquilibrium hydrogen-bond dissociation energies De for the process B HX = B + HX are calculated at the CCSD(T)(F12c)/cc-pVDZ-F12 level for B190 complexes B HX. As established earlier, De values for such complexes can be described by the equation De = cNBEA , in which NB and EHX are the nucleophilicity and electrophilicity of the Lewis base B and the Lewis acid HX, respectively, and the constant c = 1 kJ mol 1 . Graphs of De as the ordinate and EHX as the abscissa are presented for 26 series of hydrogen-bonded complexes B HX. The Lewis base is fixed and HX is HF, HCl, HBr, HI, HCN, HCCH and HCP in each series. Each plot yields a good straight line, the slope of which is the nucleophilicity NB of B. The Lewis bases are chosen for their simplicity and all have at least one non-bonding electron pair carried by the atom directly involved in the B HX hydrogen bond. The direction of the minimum value smin of the molecular electrostatic surface potential on the 0.001 e bohr 3 iso-surface in the chosen bases B usually coincides with the axis of a non-bonding electron pair. The gradient of a graph of De/smin plotted against EHX defines a reduced nucleophilicity NB = NB /smin in the sense that NB appears to be a property only of the atom of B that is directly involved in the B HX hydrogen bond, independent of the remainder of B. For example, the values of the reduced nucleophilicity for the series of isocyanide complexes CH3NC HX, HNC HX and FNC HX are 0.0343(16), 0.0337(18) and 0.0332(18), respectively, while those for the corresponding series of cyanide complexes are 0.0337(23), 0.0329(24) and 0.0333(23).A. C. L. thanks the University of Bristol for the award of a University Senior Research Fellowship. I. A. thanks the Minis- terio de Ciencia e Innovación of Spain (PGC2018-094644-B-C22 and PID2021-125207NB-C32) and Comunidad de Madrid (P2018/EMT-4329 AIRTEC-CM) for financial support.Peer reviewedRoyal Society of Chemistry (UK)Ministerio de Ciencia, Innovación y Universidades (España)Comunidad de MadridConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202220222022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501http://hdl.handle.net/10261/282261reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-094644-B-C22https://doi.org/10.1039/D2CP03999KSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2822612026-05-22T06:33:51Z
dc.title.none.fl_str_mv Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
title Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
spellingShingle Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
Alkorta, Ibon
title_short Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
title_full Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
title_fullStr Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
title_full_unstemmed Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
title_sort Reduced nucleophilicity: an intrinsic property of the Lewis base atom interacting with H in hydrogen-bonds with Lewis acids HX (X = F, Cl, Br, I, CN, CCH, CP)
dc.creator.none.fl_str_mv Alkorta, Ibon
Legon, Anthony
author Alkorta, Ibon
author_facet Alkorta, Ibon
Legon, Anthony
author_role author
author2 Legon, Anthony
author2_role author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Comunidad de Madrid
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Equilibrium hydrogen-bond dissociation energies De for the process B HX = B + HX are calculated at the CCSD(T)(F12c)/cc-pVDZ-F12 level for B190 complexes B HX. As established earlier, De values for such complexes can be described by the equation De = cNBEA , in which NB and EHX are the nucleophilicity and electrophilicity of the Lewis base B and the Lewis acid HX, respectively, and the constant c = 1 kJ mol 1 . Graphs of De as the ordinate and EHX as the abscissa are presented for 26 series of hydrogen-bonded complexes B HX. The Lewis base is fixed and HX is HF, HCl, HBr, HI, HCN, HCCH and HCP in each series. Each plot yields a good straight line, the slope of which is the nucleophilicity NB of B. The Lewis bases are chosen for their simplicity and all have at least one non-bonding electron pair carried by the atom directly involved in the B HX hydrogen bond. The direction of the minimum value smin of the molecular electrostatic surface potential on the 0.001 e bohr 3 iso-surface in the chosen bases B usually coincides with the axis of a non-bonding electron pair. The gradient of a graph of De/smin plotted against EHX defines a reduced nucleophilicity NB = NB /smin in the sense that NB appears to be a property only of the atom of B that is directly involved in the B HX hydrogen bond, independent of the remainder of B. For example, the values of the reduced nucleophilicity for the series of isocyanide complexes CH3NC HX, HNC HX and FNC HX are 0.0343(16), 0.0337(18) and 0.0332(18), respectively, while those for the corresponding series of cyanide complexes are 0.0337(23), 0.0329(24) and 0.0333(23).
publishDate 2022
dc.date.none.fl_str_mv 2022
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
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format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/282261
url http://hdl.handle.net/10261/282261
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-094644-B-C22
https://doi.org/10.1039/D2CP03999K
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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