Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy

Autores
Ismael, A.; Gomez Zavaglia, Andrea; Borba, A.; Cristiano, M. L. S.; Fausto, R.
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The amino−imino tautomerization of the nitrogen-linked conjugate 2-methyltetrazole-saccharinate (2MTS) was observed upon sublimation of the compound in vacuo. As shown previously by X-ray diffraction [Ismael, A.; Paixao, J. A.; Fausto, R.; Cristiano, M. L. S. ̃ J. Mol. Struct., 2011, 1023, 128−142], in the crystalline phase the compound exists in an amino-bridged tautomeric form. Infrared spectroscopic investigation of a cryogenic matrix prepared after sublimation of a crystalline sample of 2MTS and deposition of the sublimate together with argon (in ∼1:1000 molar ratio) onto an IR-transparent cold (15 K) substrate, revealed that the form of 2MTS present in the matrix corresponds to the theoretically predicted most stable imino-bridged tautomer. In this tautomer, the labile hydrogen atom is connected to the saccharine nitrogen, and the two heterocyclic fragments are linked by an imino moiety in which the double-bond is established with the carbon atom belonging to the saccharyl fragment. The observed isomeric form of this tautomer is characterized by a zusammen (Z) arrangement of the two rings around the CN bond of the bridging group and an intramolecular NH···N hydrogen bond. The experimental IR spectrum of the matrix-isolated 2MTS has been fully assigned based on the calculated spectra for the two most stable conformers of this tautomer. A mechanism for the conversion of the tautomeric form existing in the crystal into that present in the gas phase is proposed. As a basis for the interpretation of the experimental results, a detailed theoretical [at the DFT(B3LYP) level of approximation with the 6-31+ +G(d,p) and 6-311++G(3df,3pd)] study of the potential energy surface of the compound was performed.
Fil: Ismael, A.. Universidad de Algarve; Portugal. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones en Criotecnología de Alimentos (i); Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentina
Fil: Borba, A.. Universidad de Coimbra; Portugal
Fil: Cristiano, M. L. S.. Universidad de Algarve; Portugal
Fil: Fausto, R.. Universidad de Coimbra; Portugal
Materia
Ftir
Saccharine
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/10825
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared SpectroscopyIsmael, A.Gomez Zavaglia, AndreaBorba, A.Cristiano, M. L. S.Fausto, R.FtirSaccharinehttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2The amino−imino tautomerization of the nitrogen-linked conjugate 2-methyltetrazole-saccharinate (2MTS) was observed upon sublimation of the compound in vacuo. As shown previously by X-ray diffraction [Ismael, A.; Paixao, J. A.; Fausto, R.; Cristiano, M. L. S. ̃ J. Mol. Struct., 2011, 1023, 128−142], in the crystalline phase the compound exists in an amino-bridged tautomeric form. Infrared spectroscopic investigation of a cryogenic matrix prepared after sublimation of a crystalline sample of 2MTS and deposition of the sublimate together with argon (in ∼1:1000 molar ratio) onto an IR-transparent cold (15 K) substrate, revealed that the form of 2MTS present in the matrix corresponds to the theoretically predicted most stable imino-bridged tautomer. In this tautomer, the labile hydrogen atom is connected to the saccharine nitrogen, and the two heterocyclic fragments are linked by an imino moiety in which the double-bond is established with the carbon atom belonging to the saccharyl fragment. The observed isomeric form of this tautomer is characterized by a zusammen (Z) arrangement of the two rings around the CN bond of the bridging group and an intramolecular NH···N hydrogen bond. The experimental IR spectrum of the matrix-isolated 2MTS has been fully assigned based on the calculated spectra for the two most stable conformers of this tautomer. A mechanism for the conversion of the tautomeric form existing in the crystal into that present in the gas phase is proposed. As a basis for the interpretation of the experimental results, a detailed theoretical [at the DFT(B3LYP) level of approximation with the 6-31+ +G(d,p) and 6-311++G(3df,3pd)] study of the potential energy surface of the compound was performed.Fil: Ismael, A.. Universidad de Algarve; Portugal. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones en Criotecnología de Alimentos (i); Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; ArgentinaFil: Borba, A.. Universidad de Coimbra; PortugalFil: Cristiano, M. L. S.. Universidad de Algarve; PortugalFil: Fausto, R.. Universidad de Coimbra; PortugalAmerican Chemical Society2013-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/10825Ismael, A.; Gomez Zavaglia, Andrea; Borba, A.; Cristiano, M. L. S.; Fausto, R.; Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy; American Chemical Society; Journal Of Physical Chemistry A; 117; 15; 3-2013; 3190-31971089-56391520-5215enginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp401360cinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp401360cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:44:35Zoai:ri.conicet.gov.ar:11336/10825instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:44:35.472CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
title Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
spellingShingle Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
Ismael, A.
Ftir
Saccharine
title_short Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
title_full Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
title_fullStr Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
title_full_unstemmed Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
title_sort Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy
dc.creator.none.fl_str_mv Ismael, A.
Gomez Zavaglia, Andrea
Borba, A.
Cristiano, M. L. S.
Fausto, R.
author Ismael, A.
author_facet Ismael, A.
Gomez Zavaglia, Andrea
Borba, A.
Cristiano, M. L. S.
Fausto, R.
author_role author
author2 Gomez Zavaglia, Andrea
Borba, A.
Cristiano, M. L. S.
Fausto, R.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Ftir
Saccharine
topic Ftir
Saccharine
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The amino−imino tautomerization of the nitrogen-linked conjugate 2-methyltetrazole-saccharinate (2MTS) was observed upon sublimation of the compound in vacuo. As shown previously by X-ray diffraction [Ismael, A.; Paixao, J. A.; Fausto, R.; Cristiano, M. L. S. ̃ J. Mol. Struct., 2011, 1023, 128−142], in the crystalline phase the compound exists in an amino-bridged tautomeric form. Infrared spectroscopic investigation of a cryogenic matrix prepared after sublimation of a crystalline sample of 2MTS and deposition of the sublimate together with argon (in ∼1:1000 molar ratio) onto an IR-transparent cold (15 K) substrate, revealed that the form of 2MTS present in the matrix corresponds to the theoretically predicted most stable imino-bridged tautomer. In this tautomer, the labile hydrogen atom is connected to the saccharine nitrogen, and the two heterocyclic fragments are linked by an imino moiety in which the double-bond is established with the carbon atom belonging to the saccharyl fragment. The observed isomeric form of this tautomer is characterized by a zusammen (Z) arrangement of the two rings around the CN bond of the bridging group and an intramolecular NH···N hydrogen bond. The experimental IR spectrum of the matrix-isolated 2MTS has been fully assigned based on the calculated spectra for the two most stable conformers of this tautomer. A mechanism for the conversion of the tautomeric form existing in the crystal into that present in the gas phase is proposed. As a basis for the interpretation of the experimental results, a detailed theoretical [at the DFT(B3LYP) level of approximation with the 6-31+ +G(d,p) and 6-311++G(3df,3pd)] study of the potential energy surface of the compound was performed.
Fil: Ismael, A.. Universidad de Algarve; Portugal. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones en Criotecnología de Alimentos (i); Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentina
Fil: Borba, A.. Universidad de Coimbra; Portugal
Fil: Cristiano, M. L. S.. Universidad de Algarve; Portugal
Fil: Fausto, R.. Universidad de Coimbra; Portugal
description The amino−imino tautomerization of the nitrogen-linked conjugate 2-methyltetrazole-saccharinate (2MTS) was observed upon sublimation of the compound in vacuo. As shown previously by X-ray diffraction [Ismael, A.; Paixao, J. A.; Fausto, R.; Cristiano, M. L. S. ̃ J. Mol. Struct., 2011, 1023, 128−142], in the crystalline phase the compound exists in an amino-bridged tautomeric form. Infrared spectroscopic investigation of a cryogenic matrix prepared after sublimation of a crystalline sample of 2MTS and deposition of the sublimate together with argon (in ∼1:1000 molar ratio) onto an IR-transparent cold (15 K) substrate, revealed that the form of 2MTS present in the matrix corresponds to the theoretically predicted most stable imino-bridged tautomer. In this tautomer, the labile hydrogen atom is connected to the saccharine nitrogen, and the two heterocyclic fragments are linked by an imino moiety in which the double-bond is established with the carbon atom belonging to the saccharyl fragment. The observed isomeric form of this tautomer is characterized by a zusammen (Z) arrangement of the two rings around the CN bond of the bridging group and an intramolecular NH···N hydrogen bond. The experimental IR spectrum of the matrix-isolated 2MTS has been fully assigned based on the calculated spectra for the two most stable conformers of this tautomer. A mechanism for the conversion of the tautomeric form existing in the crystal into that present in the gas phase is proposed. As a basis for the interpretation of the experimental results, a detailed theoretical [at the DFT(B3LYP) level of approximation with the 6-31+ +G(d,p) and 6-311++G(3df,3pd)] study of the potential energy surface of the compound was performed.
publishDate 2013
dc.date.none.fl_str_mv 2013-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/10825
Ismael, A.; Gomez Zavaglia, Andrea; Borba, A.; Cristiano, M. L. S.; Fausto, R.; Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy; American Chemical Society; Journal Of Physical Chemistry A; 117; 15; 3-2013; 3190-3197
1089-5639
1520-5215
url http://hdl.handle.net/11336/10825
identifier_str_mv Ismael, A.; Gomez Zavaglia, Andrea; Borba, A.; Cristiano, M. L. S.; Fausto, R.; Amino→Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole Saccharinate as probed by Matrix Isolation Infrared Spectroscopy; American Chemical Society; Journal Of Physical Chemistry A; 117; 15; 3-2013; 3190-3197
1089-5639
1520-5215
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp401360c
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp401360c
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.8982525

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