Ab Initio, DFT and semi-empirical studies on interactions of phosphoryl, carbonyl, imino and thiocarbonyl ligands with the li+ cation: affinity and associated parameters
Autor(a) principal: | |
---|---|
Data de Publicação: | 2012 |
Outros Autores: | , |
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. |
id |
SBQ-2_3526091cfa5ba11129d461dc7baca1b1 |
---|---|
oai_identifier_str |
oai:scielo:S0103-50532012000400009 |
network_acronym_str |
SBQ-2 |
network_name_str |
Journal of the Brazilian Chemical Society (Online) |
repository_id_str |
|
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 |
format |
article |
status_str |
publishedVersion |
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 |
_version_ |
1750318173152870400 |