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 CN 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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/10825
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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 CN 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 CN 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 CN 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 |
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reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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13.144186 |