Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters

Detalhes bibliográficos
Autor(a) principal: Costa,Leonardo M. da
Data de Publicação: 2012
Outros Autores: Paes,Lílian W. C., Carneiro,José Walkimar de M.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Journal of the Brazilian Chemical Society (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000400009
Resumo: The affinity of the Li+ cation for a set of para-substituted phosphoryl, carbonyl, imino and thiocarbonyl ligands was calculated with the ab initio MP2/6-311+G(d,p), DFT B3LYP/6-311+G(d,p) and semi-empirical PM6 methods. Each set of ligand is constituted by the following para-substituted groups: NH2, OCH3, CH3, H, Cl, CN and NO2. The interaction enthalpy was calculated to quantify the affinity of the ligands for the Li+ cation. Geometric and electronic parameters were correlated with the strength of the metal-ligand interaction. The electronic nature of the para-substituted group is the main parameter that modulates the intensity of the metal-ligand binding energy. Electron donor groups make the interaction enthalpy more exothermic, whereas electron acceptor groups make the interaction enthalpy less exothermic. The energy decomposition analysis shows that the para-substituted groups modulate the intensity of the electrostatic component of the interaction without affecting the covalent component.
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spelling Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameterslithium cationsubstituent effectinteraction enthalpyEDAligand interactionThe affinity of the Li+ cation for a set of para-substituted phosphoryl, carbonyl, imino and thiocarbonyl ligands was calculated with the ab initio MP2/6-311+G(d,p), DFT B3LYP/6-311+G(d,p) and semi-empirical PM6 methods. Each set of ligand is constituted by the following para-substituted groups: NH2, OCH3, CH3, H, Cl, CN and NO2. The interaction enthalpy was calculated to quantify the affinity of the ligands for the Li+ cation. Geometric and electronic parameters were correlated with the strength of the metal-ligand interaction. The electronic nature of the para-substituted group is the main parameter that modulates the intensity of the metal-ligand binding energy. Electron donor groups make the interaction enthalpy more exothermic, whereas electron acceptor groups make the interaction enthalpy less exothermic. The energy decomposition analysis shows that the para-substituted groups modulate the intensity of the electrostatic component of the interaction without affecting the covalent component.Sociedade Brasileira de Química2012-04-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000400009Journal of the Brazilian Chemical Society v.23 n.4 2012reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532012000400009info:eu-repo/semantics/openAccessCosta,Leonardo M. daPaes,Lílian W. C.Carneiro,José Walkimar de M.eng2012-04-27T00:00:00Zoai:scielo:S0103-50532012000400009Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2012-04-27T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
title Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
spellingShingle Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
Costa,Leonardo M. da
lithium cation
substituent effect
interaction enthalpy
EDA
ligand interaction
title_short Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
title_full Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
title_fullStr Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
title_full_unstemmed Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
title_sort Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
author Costa,Leonardo M. da
author_facet Costa,Leonardo M. da
Paes,Lílian W. C.
Carneiro,José Walkimar de M.
author_role author
author2 Paes,Lílian W. C.
Carneiro,José Walkimar de M.
author2_role author
author
dc.contributor.author.fl_str_mv Costa,Leonardo M. da
Paes,Lílian W. C.
Carneiro,José Walkimar de M.
dc.subject.por.fl_str_mv lithium cation
substituent effect
interaction enthalpy
EDA
ligand interaction
topic lithium cation
substituent effect
interaction enthalpy
EDA
ligand interaction
description The affinity of the Li+ cation for a set of para-substituted phosphoryl, carbonyl, imino and thiocarbonyl ligands was calculated with the ab initio MP2/6-311+G(d,p), DFT B3LYP/6-311+G(d,p) and semi-empirical PM6 methods. Each set of ligand is constituted by the following para-substituted groups: NH2, OCH3, CH3, H, Cl, CN and NO2. The interaction enthalpy was calculated to quantify the affinity of the ligands for the Li+ cation. Geometric and electronic parameters were correlated with the strength of the metal-ligand interaction. The electronic nature of the para-substituted group is the main parameter that modulates the intensity of the metal-ligand binding energy. Electron donor groups make the interaction enthalpy more exothermic, whereas electron acceptor groups make the interaction enthalpy less exothermic. The energy decomposition analysis shows that the para-substituted groups modulate the intensity of the electrostatic component of the interaction without affecting the covalent component.
publishDate 2012
dc.date.none.fl_str_mv 2012-04-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000400009
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000400009
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0103-50532012000400009
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv text/html
dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Journal of the Brazilian Chemical Society v.23 n.4 2012
reponame:Journal of the Brazilian Chemical Society (Online)
instname:Sociedade Brasileira de Química (SBQ)
instacron:SBQ
instname_str Sociedade Brasileira de Química (SBQ)
instacron_str SBQ
institution SBQ
reponame_str Journal of the Brazilian Chemical Society (Online)
collection Journal of the Brazilian Chemical Society (Online)
repository.name.fl_str_mv Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)
repository.mail.fl_str_mv ||office@jbcs.sbq.org.br
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