Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol
Main Author: | |
---|---|
Publication Date: | 2012 |
Format: | Article |
Language: | eng |
Source: | Repositório Institucional da UFRN |
Download full: | https://repositorio.ufrn.br/jspui/handle/123456789/29213 |
Summary: | The assistance of s electron delocalization or anchimeric assistance of s electrons accounts for the large rate differences in the solvolysis of 2-exo- and 2-endo-norbornyl-p-bromobenzenesulfonates. This study was formerly analyzed by molecular orbital theory in gas phase. By revisiting this old problem from the quantum theory of atoms in molecules (QTAIM), new information on these reactions was obtained. The QTAIM results show that, in the first step of the nucleophilically unassisted solvolysis of protonated 2-exo-norbornanol and of protonated 2-endo-norbornanol, both reactions are anchimerically assisted by sigma bond participation. Similarly, in the first step of the nucleophilically unassisted solvolysis of protonated 2-endo-oxabicycloheptanol and of protonated 2-exo-oxabicycloheptanol, the QTAIM results show that both reactions are anchimerically assisted: the former from sigma bond participation from O-C bonds and valence shell electron participation from oxygen atom and the latter from sigma bond participation from C1-C2 bond. |
id |
UFRN_857455e0d6946219ac745c44f9de78a6 |
---|---|
oai_identifier_str |
oai:https://repositorio.ufrn.br:123456789/29213 |
network_acronym_str |
UFRN |
network_name_str |
Repositório Institucional da UFRN |
repository_id_str |
|
spelling |
Firme, Caio Lima2020-06-10T03:41:49Z2020-06-10T03:41:49Z2012-03FIRME, Caio Lima. Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol. Journal Of The Brazilian Chemical Society, [s. l.], v. 23, n. 3, p. 513-521, mar. 2012. ISSN 0103-5053. DOI https://doi.org/10.1590/S0103-50532012000300019. Disponível em: https://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000300019. Acesso em: 09 jun. 2020.0103-5053 (print), 1678-4790 (online)https://repositorio.ufrn.br/jspui/handle/123456789/2921310.1590/S0103-50532012000300019The assistance of s electron delocalization or anchimeric assistance of s electrons accounts for the large rate differences in the solvolysis of 2-exo- and 2-endo-norbornyl-p-bromobenzenesulfonates. This study was formerly analyzed by molecular orbital theory in gas phase. By revisiting this old problem from the quantum theory of atoms in molecules (QTAIM), new information on these reactions was obtained. The QTAIM results show that, in the first step of the nucleophilically unassisted solvolysis of protonated 2-exo-norbornanol and of protonated 2-endo-norbornanol, both reactions are anchimerically assisted by sigma bond participation. Similarly, in the first step of the nucleophilically unassisted solvolysis of protonated 2-endo-oxabicycloheptanol and of protonated 2-exo-oxabicycloheptanol, the QTAIM results show that both reactions are anchimerically assisted: the former from sigma bond participation from O-C bonds and valence shell electron participation from oxygen atom and the latter from sigma bond participation from C1-C2 bond.A assistência da deslocalização de elétrons sigma ou assistência anquimérica dos elétrons sigma explica grandes diferenças de velocidade na solvólise de 2-exo- e 2-endo-norbornil-p-bromobenzenosulfonatos. Este estudo foi anteriormente analisado pela teoria dos orbitais moleculares em fase gás. Ao revisitar este antigo problema a partir da teoria quântica de átomos em moléculas (QTAIM), novas informações sobre essas reações foram obtidas. Os resultados de QTAIM mostram que, na primeira etapa da solvólise não assistida nucleofilicamente dos alcoóis protonados 2-exo-norbornanol e 2-endo-norbornanol, ambas as reações são anquimericamente assistidas pela participação de elétrons sigma. Similarmente, na primeira etapa da solvólise não assistida nucleofilicamente dos álcoois protonados 2-endo-oxabicicloheptanol e 2-exo-oxabicicloheptanol, os resultados de QTAIM mostram que ambas as reações são anquimericamente assistidas: a primeira a partir da participação da ligação sigma C-O e de pares de elétrons isolados do oxigênio e a última a partir da participação da ligação sigma C1-C2.Sociedade Brasileira de QuímicaAttribution-NonCommercial 3.0 Brazilhttp://creativecommons.org/licenses/by-nc/3.0/br/info:eu-repo/semantics/openAccessQTAIM2-norbornyl cationSigma bond participation2-oxabicycloheptanolSolvolysisTopological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanolinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleengreponame:Repositório Institucional da UFRNinstname:Universidade Federal do Rio Grande do Norte (UFRN)instacron:UFRNORIGINALTopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdfTopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdfapplication/pdf1065000https://repositorio.ufrn.br/bitstream/123456789/29213/1/TopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf5d2669bb7740af2dd527665287a4e67aMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8920https://repositorio.ufrn.br/bitstream/123456789/29213/2/license_rdf728dfda2fa81b274c619d08d1dfc1a03MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81484https://repositorio.ufrn.br/bitstream/123456789/29213/3/license.txte9597aa2854d128fd968be5edc8a28d9MD53TEXTTopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.txtTopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.txtExtracted texttext/plain34985https://repositorio.ufrn.br/bitstream/123456789/29213/4/TopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.txt80349818a233c782066e4022cdaf591cMD54THUMBNAILTopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.jpgTopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.jpgGenerated Thumbnailimage/jpeg1653https://repositorio.ufrn.br/bitstream/123456789/29213/5/TopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.jpg1b8f86f31d16d09839327244fb6f2b11MD55123456789/292132021-02-15 16:08:20.838oai:https://repositorio.ufrn.br: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Repositório de PublicaçõesPUBhttp://repositorio.ufrn.br/oai/opendoar:2021-02-15T19:08:20Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)false |
dc.title.pt_BR.fl_str_mv |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
title |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
spellingShingle |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol Firme, Caio Lima QTAIM 2-norbornyl cation Sigma bond participation 2-oxabicycloheptanol Solvolysis |
title_short |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
title_full |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
title_fullStr |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
title_full_unstemmed |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
title_sort |
Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol |
author |
Firme, Caio Lima |
author_facet |
Firme, Caio Lima |
author_role |
author |
dc.contributor.author.fl_str_mv |
Firme, Caio Lima |
dc.subject.por.fl_str_mv |
QTAIM 2-norbornyl cation Sigma bond participation 2-oxabicycloheptanol Solvolysis |
topic |
QTAIM 2-norbornyl cation Sigma bond participation 2-oxabicycloheptanol Solvolysis |
description |
The assistance of s electron delocalization or anchimeric assistance of s electrons accounts for the large rate differences in the solvolysis of 2-exo- and 2-endo-norbornyl-p-bromobenzenesulfonates. This study was formerly analyzed by molecular orbital theory in gas phase. By revisiting this old problem from the quantum theory of atoms in molecules (QTAIM), new information on these reactions was obtained. The QTAIM results show that, in the first step of the nucleophilically unassisted solvolysis of protonated 2-exo-norbornanol and of protonated 2-endo-norbornanol, both reactions are anchimerically assisted by sigma bond participation. Similarly, in the first step of the nucleophilically unassisted solvolysis of protonated 2-endo-oxabicycloheptanol and of protonated 2-exo-oxabicycloheptanol, the QTAIM results show that both reactions are anchimerically assisted: the former from sigma bond participation from O-C bonds and valence shell electron participation from oxygen atom and the latter from sigma bond participation from C1-C2 bond. |
publishDate |
2012 |
dc.date.issued.fl_str_mv |
2012-03 |
dc.date.accessioned.fl_str_mv |
2020-06-10T03:41:49Z |
dc.date.available.fl_str_mv |
2020-06-10T03:41:49Z |
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. Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol. Journal Of The Brazilian Chemical Society, [s. l.], v. 23, n. 3, p. 513-521, mar. 2012. ISSN 0103-5053. DOI https://doi.org/10.1590/S0103-50532012000300019. Disponível em: https://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000300019. Acesso em: 09 jun. 2020. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufrn.br/jspui/handle/123456789/29213 |
dc.identifier.issn.none.fl_str_mv |
0103-5053 (print), 1678-4790 (online) |
dc.identifier.doi.none.fl_str_mv |
10.1590/S0103-50532012000300019 |
identifier_str_mv |
FIRME, Caio Lima. Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol. Journal Of The Brazilian Chemical Society, [s. l.], v. 23, n. 3, p. 513-521, mar. 2012. ISSN 0103-5053. DOI https://doi.org/10.1590/S0103-50532012000300019. Disponível em: https://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532012000300019. Acesso em: 09 jun. 2020. 0103-5053 (print), 1678-4790 (online) 10.1590/S0103-50532012000300019 |
url |
https://repositorio.ufrn.br/jspui/handle/123456789/29213 |
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/123456789/29213/1/TopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf https://repositorio.ufrn.br/bitstream/123456789/29213/2/license_rdf https://repositorio.ufrn.br/bitstream/123456789/29213/3/license.txt https://repositorio.ufrn.br/bitstream/123456789/29213/4/TopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.txt https://repositorio.ufrn.br/bitstream/123456789/29213/5/TopologicalStudyFirstStepNucleophilicallyUnassisted_Firme_2012.pdf.jpg |
bitstream.checksum.fl_str_mv |
5d2669bb7740af2dd527665287a4e67a 728dfda2fa81b274c619d08d1dfc1a03 e9597aa2854d128fd968be5edc8a28d9 80349818a233c782066e4022cdaf591c 1b8f86f31d16d09839327244fb6f2b11 |
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_ |
1797777186044772352 |