A theoretical HSAB study of the acidity of carbon acids CH3Z

Detalhes bibliográficos
Autor(a) principal: Rezende,Marcos C.
Data de Publicação: 2001
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=S0103-50532001000100010
Resumo: The gas-phase acidity of nine carbon acids of the form CH3Z (nitromethane, acetophenone, dimethylsulfone, acetaldehyde, butanone, acetone, methyl acetate, acetonitrile and dimethylsulfoxide) was investigated, in the search of correlations with global and local HSAB properties, calculated at the 3-21G, 6-31G* and 6-31+G(3df,2p) levels. A reasonable correlation was obtained with the calculated ionization energies. Based on the obtained correlation, the gas-phase acidity of methyl thioacetate was estimated (deltaG°= 1476 kJ mol-1) as close to that of the most acidic member of the series, nitromethane. The nucleophilic Fukui functions of the hard and soft anionic centers in each base - CH2Z stabilized by direct conjugation were calculated, following two different approaches, and their ratios utilized to interpret the shifts in acidity when the acids are transferred from gas-phase to aqueous solution.
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spelling A theoretical HSAB study of the acidity of carbon acids CH3Zaciditycarbon acidsHSAB theoryFukui functionsThe gas-phase acidity of nine carbon acids of the form CH3Z (nitromethane, acetophenone, dimethylsulfone, acetaldehyde, butanone, acetone, methyl acetate, acetonitrile and dimethylsulfoxide) was investigated, in the search of correlations with global and local HSAB properties, calculated at the 3-21G, 6-31G* and 6-31+G(3df,2p) levels. A reasonable correlation was obtained with the calculated ionization energies. Based on the obtained correlation, the gas-phase acidity of methyl thioacetate was estimated (deltaG°= 1476 kJ mol-1) as close to that of the most acidic member of the series, nitromethane. The nucleophilic Fukui functions of the hard and soft anionic centers in each base - CH2Z stabilized by direct conjugation were calculated, following two different approaches, and their ratios utilized to interpret the shifts in acidity when the acids are transferred from gas-phase to aqueous solution.Sociedade Brasileira de Química2001-01-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000100010Journal of the Brazilian Chemical Society v.12 n.1 2001reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532001000100010info:eu-repo/semantics/openAccessRezende,Marcos C.eng2001-04-19T00:00:00Zoai:scielo:S0103-50532001000100010Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2001-04-19T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv A theoretical HSAB study of the acidity of carbon acids CH3Z
title A theoretical HSAB study of the acidity of carbon acids CH3Z
spellingShingle A theoretical HSAB study of the acidity of carbon acids CH3Z
Rezende,Marcos C.
acidity
carbon acids
HSAB theory
Fukui functions
title_short A theoretical HSAB study of the acidity of carbon acids CH3Z
title_full A theoretical HSAB study of the acidity of carbon acids CH3Z
title_fullStr A theoretical HSAB study of the acidity of carbon acids CH3Z
title_full_unstemmed A theoretical HSAB study of the acidity of carbon acids CH3Z
title_sort A theoretical HSAB study of the acidity of carbon acids CH3Z
author Rezende,Marcos C.
author_facet Rezende,Marcos C.
author_role author
dc.contributor.author.fl_str_mv Rezende,Marcos C.
dc.subject.por.fl_str_mv acidity
carbon acids
HSAB theory
Fukui functions
topic acidity
carbon acids
HSAB theory
Fukui functions
description The gas-phase acidity of nine carbon acids of the form CH3Z (nitromethane, acetophenone, dimethylsulfone, acetaldehyde, butanone, acetone, methyl acetate, acetonitrile and dimethylsulfoxide) was investigated, in the search of correlations with global and local HSAB properties, calculated at the 3-21G, 6-31G* and 6-31+G(3df,2p) levels. A reasonable correlation was obtained with the calculated ionization energies. Based on the obtained correlation, the gas-phase acidity of methyl thioacetate was estimated (deltaG°= 1476 kJ mol-1) as close to that of the most acidic member of the series, nitromethane. The nucleophilic Fukui functions of the hard and soft anionic centers in each base - CH2Z stabilized by direct conjugation were calculated, following two different approaches, and their ratios utilized to interpret the shifts in acidity when the acids are transferred from gas-phase to aqueous solution.
publishDate 2001
dc.date.none.fl_str_mv 2001-01-01
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=S0103-50532001000100010
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000100010
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0103-50532001000100010
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.12 n.1 2001
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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