Identification of carbonium and carbenium ions by QTAIM

Detalhes bibliográficos
Autor(a) principal: Firme, Caio Lima
Data de Publicação: 2009
Outros Autores: Antunes, Octavio Augusto Ceva, Esteves, Pierre Mothé
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UFRN
Texto Completo: https://repositorio.ufrn.br/handle/123456789/31553
Resumo: The Gassman-Fentiman tool of increasing electron demand was used to identify carbonium and carbenium ions. Nonetheless, due to its ambiguous understanding, it was pivot of a historical dispute. We applied the Quantum Theory of Atoms in Molecules (QTAIM) metodology to characterize the carbonium and carbenium ions on an easier and more effective way. By comparing selected topological information of reference carbenium ions the QTAIM metodology can be used to evaluate whether a carbocation is classical or not. In addition, it is possible to rank a set of carbonium ions in order of their corresponding σ or π delocalization. There are few differences between our QTAIM-based model and Gassman-Fentiman tool. Unlike Gassman-Fentiman tool results, 7-anisyl-7-norbornenyl and 2-anisyl-2-norbornyl cations are non-classical, although they are the least nonclassical ions in their corresponding set of studied cations.
id UFRN_7ef4e6bd86fbe4b004faaf3113fee407
oai_identifier_str oai:https://repositorio.ufrn.br:123456789/31553
network_acronym_str UFRN
network_name_str Repositório Institucional da UFRN
repository_id_str
spelling Firme, Caio LimaAntunes, Octavio Augusto CevaEsteves, Pierre Mothé2021-02-18T22:06:52Z2021-02-18T22:06:52Z2009FIRME, Caio Lima; ANTUNES, Octavio Augusto Ceva; ESTEVES, Pierre Mothé. Identification of carbonium and carbenium ions by QTAIM. Journal Of The Brazilian Chemical Society, [S.l.], v. 20, n. 3, p. 543-548, 2009. Disponível em: https://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532009000300020. Acesso em: 14 maio 2020. https://doi.org/10.1590/S0103-505320090003000201678-4790https://repositorio.ufrn.br/handle/123456789/3155310.1590/S0103-50532009000300020The Gassman-Fentiman tool of increasing electron demand was used to identify carbonium and carbenium ions. Nonetheless, due to its ambiguous understanding, it was pivot of a historical dispute. We applied the Quantum Theory of Atoms in Molecules (QTAIM) metodology to characterize the carbonium and carbenium ions on an easier and more effective way. By comparing selected topological information of reference carbenium ions the QTAIM metodology can be used to evaluate whether a carbocation is classical or not. In addition, it is possible to rank a set of carbonium ions in order of their corresponding σ or π delocalization. There are few differences between our QTAIM-based model and Gassman-Fentiman tool. Unlike Gassman-Fentiman tool results, 7-anisyl-7-norbornenyl and 2-anisyl-2-norbornyl cations are non-classical, although they are the least nonclassical ions in their corresponding set of studied cations.A ferramenta de Gassman-Fentiman da demanda crescente de elétrons foi usada para identificar íons carbênios e íons carbônios. Contudo, devido ao seu entendimento ambíguo, ela foi pivô de uma disputa histórica. Nós aplicamos a metodologia da Teoria Quântica de Átomos em Moléculas - QTAIM - para caracterizar íons carbênios e íons carbônios de uma forma mais eficaz e mais fácil. Essa metodologia pode ser usada para avaliar se um carbocátion é clássico ou não. Além disso, é possível classificar um conjunto de íon carbônio na ordem de magnitude da deslocalização σ, ou π. Há poucas diferenças entre os resultados de nosso modelo baseado na QTAIM e da ferramenta de Gassman-Fentiman. Contudo, diferentemente da ferramenta de Gassman-Fentiman, os cátions 7-anisol-7-norbornenila e 2-anisol-2-norbornila são não-clássicos, embora sejam os menos íons não-clássicos em seus conjuntos correspondentes de cátions estudados.Sociedade Brasileira de QuímicaAttribution-NonCommercial 3.0 Brazilhttp://creativecommons.org/licenses/by-nc/3.0/br/info:eu-repo/semantics/openAccessNorbornyl cationNorbornenyl cationQTAIMCarbonium ionCarbenium ionIdentification of carbonium and carbenium ions by QTAIMinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleengreponame:Repositório Institucional da UFRNinstname:Universidade Federal do Rio Grande do Norte (UFRN)instacron:UFRNORIGINALIdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdfIdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdfapplication/pdf1328827https://repositorio.ufrn.br/bitstream/123456789/31553/1/IdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf4147f2d8b1f34ef951d4d7f135861c85MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8920https://repositorio.ufrn.br/bitstream/123456789/31553/4/license_rdf728dfda2fa81b274c619d08d1dfc1a03MD54LICENSElicense.txtlicense.txttext/plain; charset=utf-81484https://repositorio.ufrn.br/bitstream/123456789/31553/5/license.txte9597aa2854d128fd968be5edc8a28d9MD55TEXTIdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.txtIdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.txtExtracted texttext/plain39917https://repositorio.ufrn.br/bitstream/123456789/31553/6/IdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.txt1a621d738ca217ed2c038955818a2442MD56THUMBNAILIdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.jpgIdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.jpgGenerated Thumbnailimage/jpeg1581https://repositorio.ufrn.br/bitstream/123456789/31553/7/IdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.jpg02c80357f1438bfa0276cc9ca9f1f8eaMD57123456789/315532021-02-21 05:31:16.387oai:https://repositorio.ufrn.br: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Repositório de PublicaçõesPUBhttp://repositorio.ufrn.br/oai/opendoar:2021-02-21T08:31:16Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)false
dc.title.pt_BR.fl_str_mv Identification of carbonium and carbenium ions by QTAIM
title Identification of carbonium and carbenium ions by QTAIM
spellingShingle Identification of carbonium and carbenium ions by QTAIM
Firme, Caio Lima
Norbornyl cation
Norbornenyl cation
QTAIM
Carbonium ion
Carbenium ion
title_short Identification of carbonium and carbenium ions by QTAIM
title_full Identification of carbonium and carbenium ions by QTAIM
title_fullStr Identification of carbonium and carbenium ions by QTAIM
title_full_unstemmed Identification of carbonium and carbenium ions by QTAIM
title_sort Identification of carbonium and carbenium ions by QTAIM
author Firme, Caio Lima
author_facet Firme, Caio Lima
Antunes, Octavio Augusto Ceva
Esteves, Pierre Mothé
author_role author
author2 Antunes, Octavio Augusto Ceva
Esteves, Pierre Mothé
author2_role author
author
dc.contributor.author.fl_str_mv Firme, Caio Lima
Antunes, Octavio Augusto Ceva
Esteves, Pierre Mothé
dc.subject.por.fl_str_mv Norbornyl cation
Norbornenyl cation
QTAIM
Carbonium ion
Carbenium ion
topic Norbornyl cation
Norbornenyl cation
QTAIM
Carbonium ion
Carbenium ion
description The Gassman-Fentiman tool of increasing electron demand was used to identify carbonium and carbenium ions. Nonetheless, due to its ambiguous understanding, it was pivot of a historical dispute. We applied the Quantum Theory of Atoms in Molecules (QTAIM) metodology to characterize the carbonium and carbenium ions on an easier and more effective way. By comparing selected topological information of reference carbenium ions the QTAIM metodology can be used to evaluate whether a carbocation is classical or not. In addition, it is possible to rank a set of carbonium ions in order of their corresponding σ or π delocalization. There are few differences between our QTAIM-based model and Gassman-Fentiman tool. Unlike Gassman-Fentiman tool results, 7-anisyl-7-norbornenyl and 2-anisyl-2-norbornyl cations are non-classical, although they are the least nonclassical ions in their corresponding set of studied cations.
publishDate 2009
dc.date.issued.fl_str_mv 2009
dc.date.accessioned.fl_str_mv 2021-02-18T22:06:52Z
dc.date.available.fl_str_mv 2021-02-18T22:06:52Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.citation.fl_str_mv FIRME, Caio Lima; ANTUNES, Octavio Augusto Ceva; ESTEVES, Pierre Mothé. Identification of carbonium and carbenium ions by QTAIM. Journal Of The Brazilian Chemical Society, [S.l.], v. 20, n. 3, p. 543-548, 2009. Disponível em: https://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532009000300020. Acesso em: 14 maio 2020. https://doi.org/10.1590/S0103-50532009000300020
dc.identifier.uri.fl_str_mv https://repositorio.ufrn.br/handle/123456789/31553
dc.identifier.issn.none.fl_str_mv 1678-4790
dc.identifier.doi.none.fl_str_mv 10.1590/S0103-50532009000300020
identifier_str_mv FIRME, Caio Lima; ANTUNES, Octavio Augusto Ceva; ESTEVES, Pierre Mothé. Identification of carbonium and carbenium ions by QTAIM. Journal Of The Brazilian Chemical Society, [S.l.], v. 20, n. 3, p. 543-548, 2009. Disponível em: https://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532009000300020. Acesso em: 14 maio 2020. https://doi.org/10.1590/S0103-50532009000300020
1678-4790
10.1590/S0103-50532009000300020
url https://repositorio.ufrn.br/handle/123456789/31553
dc.language.iso.fl_str_mv eng
language eng
dc.rights.driver.fl_str_mv Attribution-NonCommercial 3.0 Brazil
http://creativecommons.org/licenses/by-nc/3.0/br/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial 3.0 Brazil
http://creativecommons.org/licenses/by-nc/3.0/br/
eu_rights_str_mv openAccess
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 reponame:Repositório Institucional da UFRN
instname:Universidade Federal do Rio Grande do Norte (UFRN)
instacron:UFRN
instname_str Universidade Federal do Rio Grande do Norte (UFRN)
instacron_str UFRN
institution UFRN
reponame_str Repositório Institucional da UFRN
collection Repositório Institucional da UFRN
bitstream.url.fl_str_mv https://repositorio.ufrn.br/bitstream/123456789/31553/1/IdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf
https://repositorio.ufrn.br/bitstream/123456789/31553/4/license_rdf
https://repositorio.ufrn.br/bitstream/123456789/31553/5/license.txt
https://repositorio.ufrn.br/bitstream/123456789/31553/6/IdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.txt
https://repositorio.ufrn.br/bitstream/123456789/31553/7/IdentificationCarboniumCarbeniumIonsQTAIM_Firme_2009.pdf.jpg
bitstream.checksum.fl_str_mv 4147f2d8b1f34ef951d4d7f135861c85
728dfda2fa81b274c619d08d1dfc1a03
e9597aa2854d128fd968be5edc8a28d9
1a621d738ca217ed2c038955818a2442
02c80357f1438bfa0276cc9ca9f1f8ea
bitstream.checksumAlgorithm.fl_str_mv MD5
MD5
MD5
MD5
MD5
repository.name.fl_str_mv Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)
repository.mail.fl_str_mv
_version_ 1797777128627896320

Registros relacionados