S-H rotamerization via tunneling in a thiol form of thioacetamide
Autor(a) principal: | |
---|---|
Data de Publicação: | 2019 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/101237 https://doi.org/10.1039/c9cp03417j |
Resumo: | Rotamerization of a hydroxyl (O-H) group by tunneling is well-known and has been extensively studied. On the other hand, similar tunneling processes for the thiol (S-H) group have not been reported yet. In this work, the imino-thiol forms of thioacetamide were studied in cryogenic matrices (Ar, Xe) after UV-irradiation of the common amino-thione form of the compound. Four different imino-thiol forms were generated, corresponding to the cis or trans thiol (C/T) conformers of the two imino isomers (syn and anti; s/a). Noteworthy, the syn-cis (sC) imino-thiol form was found to convert spontaneously to the syn-trans (sT) form (with a half-life of 80 min), in a process whose reaction rate is independent of the temperature (i.e., at 11 or 20 K). Such conformational transformation represents the first experimental observation of an S-H rotamerization occurring by tunneling. Computations based on the Wentzel-Kramers-Brillouin formalism predict a tunneling half-life for the S-H rotamerization of syn-imino sC to sT on the time scale of minutes, in agreement with the experimental observations. |
id |
RCAP_ca9070cf513a0ca3ef058fc55ed25dc8 |
---|---|
oai_identifier_str |
oai:estudogeral.uc.pt:10316/101237 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
spelling |
S-H rotamerization via tunneling in a thiol form of thioacetamideRotamerization of a hydroxyl (O-H) group by tunneling is well-known and has been extensively studied. On the other hand, similar tunneling processes for the thiol (S-H) group have not been reported yet. In this work, the imino-thiol forms of thioacetamide were studied in cryogenic matrices (Ar, Xe) after UV-irradiation of the common amino-thione form of the compound. Four different imino-thiol forms were generated, corresponding to the cis or trans thiol (C/T) conformers of the two imino isomers (syn and anti; s/a). Noteworthy, the syn-cis (sC) imino-thiol form was found to convert spontaneously to the syn-trans (sT) form (with a half-life of 80 min), in a process whose reaction rate is independent of the temperature (i.e., at 11 or 20 K). Such conformational transformation represents the first experimental observation of an S-H rotamerization occurring by tunneling. Computations based on the Wentzel-Kramers-Brillouin formalism predict a tunneling half-life for the S-H rotamerization of syn-imino sC to sT on the time scale of minutes, in agreement with the experimental observations.Royal Society of Chemistry2019-08-21info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/101237http://hdl.handle.net/10316/101237https://doi.org/10.1039/c9cp03417jenghttps://doi.org/10.1039/C9CP03417JGóbi, SándorNunes, Cláudio MReva, IgorTarczay, GyörgyFausto, Ruiinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2022-08-17T23:02:43Zoai:estudogeral.uc.pt:10316/101237Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:18:27.801918Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
title |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
spellingShingle |
S-H rotamerization via tunneling in a thiol form of thioacetamide Góbi, Sándor |
title_short |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
title_full |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
title_fullStr |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
title_full_unstemmed |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
title_sort |
S-H rotamerization via tunneling in a thiol form of thioacetamide |
author |
Góbi, Sándor |
author_facet |
Góbi, Sándor Nunes, Cláudio M Reva, Igor Tarczay, György Fausto, Rui |
author_role |
author |
author2 |
Nunes, Cláudio M Reva, Igor Tarczay, György Fausto, Rui |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Góbi, Sándor Nunes, Cláudio M Reva, Igor Tarczay, György Fausto, Rui |
description |
Rotamerization of a hydroxyl (O-H) group by tunneling is well-known and has been extensively studied. On the other hand, similar tunneling processes for the thiol (S-H) group have not been reported yet. In this work, the imino-thiol forms of thioacetamide were studied in cryogenic matrices (Ar, Xe) after UV-irradiation of the common amino-thione form of the compound. Four different imino-thiol forms were generated, corresponding to the cis or trans thiol (C/T) conformers of the two imino isomers (syn and anti; s/a). Noteworthy, the syn-cis (sC) imino-thiol form was found to convert spontaneously to the syn-trans (sT) form (with a half-life of 80 min), in a process whose reaction rate is independent of the temperature (i.e., at 11 or 20 K). Such conformational transformation represents the first experimental observation of an S-H rotamerization occurring by tunneling. Computations based on the Wentzel-Kramers-Brillouin formalism predict a tunneling half-life for the S-H rotamerization of syn-imino sC to sT on the time scale of minutes, in agreement with the experimental observations. |
publishDate |
2019 |
dc.date.none.fl_str_mv |
2019-08-21 |
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.uri.fl_str_mv |
http://hdl.handle.net/10316/101237 http://hdl.handle.net/10316/101237 https://doi.org/10.1039/c9cp03417j |
url |
http://hdl.handle.net/10316/101237 https://doi.org/10.1039/c9cp03417j |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
https://doi.org/10.1039/C9CP03417J |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
|
_version_ |
1799134079138922496 |