Identification of carbonium and carbenium ions by QTAIM
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Publication Date: | 2009 |
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Format: | Article |
Language: | eng |
Source: | Repositório Institucional da UFRN |
Download full: | https://repositorio.ufrn.br/handle/123456789/31553 |
Summary: | 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. |
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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 |
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eng |
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Attribution-NonCommercial 3.0 Brazil http://creativecommons.org/licenses/by-nc/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial 3.0 Brazil http://creativecommons.org/licenses/by-nc/3.0/br/ |
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openAccess |
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Sociedade Brasileira de Química |
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Sociedade Brasileira de Química |
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UFRN |
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UFRN |
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Repositório Institucional da UFRN |
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Repositório Institucional da UFRN |
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