Photochemistry of 1-phenyl-tetrazolone isolated in solid argon

Autores
Gomez Zavaglia, Andrea; Reva, Igor D.; Frija, Luis M.T.; Cristiano, María Lurdes; Fausto, Rui
Año de publicación
2006
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The molecular structure, vibrational spectra, tautomerism and photochemistry of the derivative of tetrazole, 1-phenyl-tetrazolone (C7H6N4O;PT) have been studied by FT-IR matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations. Among the five structures in which PT could be expected to exist (two keto tautomers, one mesoionic olate-form and two different conformers of the hydroxyl tautomer), only the most stable species, 1-phenyl-1,4-dihydro-5H-tetrazol-5-one, could be experimentally observed in low temperature argon matrices. Monomers of this tautomer give rise to an IR spectrum that fits nicely the calculated spectrum obtained at the DFT/B3LYP/6-311++G(d,p) level of theory. In situ UV irradiation (λ > 235 nm) of the matrix-isolated PT induces three main photochemical processes, all of them involving cleavage of the tetrazolering: e.g. (1) molecular nitrogen loss, with production of 1-phenyl- diaziridin-3-one; this compound reacts subsequently to form 1-aza-1,2,4,6- cycloheptatetraene and isocyanic acid (eventually, also to form CO plus phenyldiazene); (2) cleavage of the C(5)–N(1) and N(3)–N(4) tetrazole-ring bonds, with production of phenylazide and isocyanic acid, with phenylazide then losingN2 to yield as final product 1-aza-1,2,4,6-cycloheptatetraene; and (3) cleavage of the N(1)–N(2) and N(4)–C(5) tetrazole-ring bonds, to yield phenylisocyanate and azide. The observed photochemical processes are distinct from the preferred thermal fragmentation channel, where CO is produced together with a weak IR absorbant species.
Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Reva, Igor D.. Universidad de Coimbra; Portugal
Fil: Frija, Luis M.T.. Universidad de Algarve; Portugal
Fil: Cristiano, María Lurdes. Universidad de Algarve; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
Phenyl-tetrazolone
1-Aza-1,2,4,6-cycloheptatetraene
Phenyldiazene
Phenylisocyanate
Azide
Isocyanic acid
Tetrazole-ring cleavage
Matrix isolation IR spectroscopy
Photochemical fragmentation
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:11336/116103
Acceder
id CONICETDig_c06be935c46f51fcd810fdef534a7e33
oai_identifier_str oai:ri.conicet.gov.ar:11336/116103
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photochemistry of 1-phenyl-tetrazolone isolated in solid argonGomez Zavaglia, AndreaReva, Igor D.Frija, Luis M.T.Cristiano, María LurdesFausto, RuiPhenyl-tetrazolone1-Aza-1,2,4,6-cycloheptatetraenePhenyldiazenePhenylisocyanateAzideIsocyanic acidTetrazole-ring cleavageMatrix isolation IR spectroscopyPhotochemical fragmentationhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2The molecular structure, vibrational spectra, tautomerism and photochemistry of the derivative of tetrazole, 1-phenyl-tetrazolone (C7H6N4O;PT) have been studied by FT-IR matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations. Among the five structures in which PT could be expected to exist (two keto tautomers, one mesoionic olate-form and two different conformers of the hydroxyl tautomer), only the most stable species, 1-phenyl-1,4-dihydro-5H-tetrazol-5-one, could be experimentally observed in low temperature argon matrices. Monomers of this tautomer give rise to an IR spectrum that fits nicely the calculated spectrum obtained at the DFT/B3LYP/6-311++G(d,p) level of theory. In situ UV irradiation (λ > 235 nm) of the matrix-isolated PT induces three main photochemical processes, all of them involving cleavage of the tetrazolering: e.g. (1) molecular nitrogen loss, with production of 1-phenyl- diaziridin-3-one; this compound reacts subsequently to form 1-aza-1,2,4,6- cycloheptatetraene and isocyanic acid (eventually, also to form CO plus phenyldiazene); (2) cleavage of the C(5)–N(1) and N(3)–N(4) tetrazole-ring bonds, with production of phenylazide and isocyanic acid, with phenylazide then losingN2 to yield as final product 1-aza-1,2,4,6-cycloheptatetraene; and (3) cleavage of the N(1)–N(2) and N(4)–C(5) tetrazole-ring bonds, to yield phenylisocyanate and azide. The observed photochemical processes are distinct from the preferred thermal fragmentation channel, where CO is produced together with a weak IR absorbant species.Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaFil: Reva, Igor D.. Universidad de Coimbra; PortugalFil: Frija, Luis M.T.. Universidad de Algarve; PortugalFil: Cristiano, María Lurdes. Universidad de Algarve; PortugalFil: Fausto, Rui. Universidad de Coimbra; PortugalElsevier Science Sa2006-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/116103Gomez Zavaglia, Andrea; Reva, Igor D.; Frija, Luis M.T.; Cristiano, María Lurdes; Fausto, Rui; Photochemistry of 1-phenyl-tetrazolone isolated in solid argon; Elsevier Science Sa; Journal of Photochemistry and Photobiology A: Chemistry; 179; 3; 12-2006; 243-2551010-60301873-2666CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jphotochem.2005.08.021info:eu-repo/semantics/altIdentifier/url/https://tinyurl.com/y5ep9ogbinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:01:26Zoai:ri.conicet.gov.ar:11336/116103instacron: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:34982025-09-03 10:01:27.08CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
title Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
spellingShingle Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
Gomez Zavaglia, Andrea
Phenyl-tetrazolone
1-Aza-1,2,4,6-cycloheptatetraene
Phenyldiazene
Phenylisocyanate
Azide
Isocyanic acid
Tetrazole-ring cleavage
Matrix isolation IR spectroscopy
Photochemical fragmentation
title_short Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
title_full Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
title_fullStr Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
title_full_unstemmed Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
title_sort Photochemistry of 1-phenyl-tetrazolone isolated in solid argon
dc.creator.none.fl_str_mv Gomez Zavaglia, Andrea
Reva, Igor D.
Frija, Luis M.T.
Cristiano, María Lurdes
Fausto, Rui
author Gomez Zavaglia, Andrea
author_facet Gomez Zavaglia, Andrea
Reva, Igor D.
Frija, Luis M.T.
Cristiano, María Lurdes
Fausto, Rui
author_role author
author2 Reva, Igor D.
Frija, Luis M.T.
Cristiano, María Lurdes
Fausto, Rui
author2_role author
author
author
author
dc.subject.none.fl_str_mv Phenyl-tetrazolone
1-Aza-1,2,4,6-cycloheptatetraene
Phenyldiazene
Phenylisocyanate
Azide
Isocyanic acid
Tetrazole-ring cleavage
Matrix isolation IR spectroscopy
Photochemical fragmentation
topic Phenyl-tetrazolone
1-Aza-1,2,4,6-cycloheptatetraene
Phenyldiazene
Phenylisocyanate
Azide
Isocyanic acid
Tetrazole-ring cleavage
Matrix isolation IR spectroscopy
Photochemical fragmentation
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 molecular structure, vibrational spectra, tautomerism and photochemistry of the derivative of tetrazole, 1-phenyl-tetrazolone (C7H6N4O;PT) have been studied by FT-IR matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations. Among the five structures in which PT could be expected to exist (two keto tautomers, one mesoionic olate-form and two different conformers of the hydroxyl tautomer), only the most stable species, 1-phenyl-1,4-dihydro-5H-tetrazol-5-one, could be experimentally observed in low temperature argon matrices. Monomers of this tautomer give rise to an IR spectrum that fits nicely the calculated spectrum obtained at the DFT/B3LYP/6-311++G(d,p) level of theory. In situ UV irradiation (λ > 235 nm) of the matrix-isolated PT induces three main photochemical processes, all of them involving cleavage of the tetrazolering: e.g. (1) molecular nitrogen loss, with production of 1-phenyl- diaziridin-3-one; this compound reacts subsequently to form 1-aza-1,2,4,6- cycloheptatetraene and isocyanic acid (eventually, also to form CO plus phenyldiazene); (2) cleavage of the C(5)–N(1) and N(3)–N(4) tetrazole-ring bonds, with production of phenylazide and isocyanic acid, with phenylazide then losingN2 to yield as final product 1-aza-1,2,4,6-cycloheptatetraene; and (3) cleavage of the N(1)–N(2) and N(4)–C(5) tetrazole-ring bonds, to yield phenylisocyanate and azide. The observed photochemical processes are distinct from the preferred thermal fragmentation channel, where CO is produced together with a weak IR absorbant species.
Fil: Gomez Zavaglia, Andrea. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Universidad de Coimbra; Portugal. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Reva, Igor D.. Universidad de Coimbra; Portugal
Fil: Frija, Luis M.T.. Universidad de Algarve; Portugal
Fil: Cristiano, María Lurdes. Universidad de Algarve; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description The molecular structure, vibrational spectra, tautomerism and photochemistry of the derivative of tetrazole, 1-phenyl-tetrazolone (C7H6N4O;PT) have been studied by FT-IR matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations. Among the five structures in which PT could be expected to exist (two keto tautomers, one mesoionic olate-form and two different conformers of the hydroxyl tautomer), only the most stable species, 1-phenyl-1,4-dihydro-5H-tetrazol-5-one, could be experimentally observed in low temperature argon matrices. Monomers of this tautomer give rise to an IR spectrum that fits nicely the calculated spectrum obtained at the DFT/B3LYP/6-311++G(d,p) level of theory. In situ UV irradiation (λ > 235 nm) of the matrix-isolated PT induces three main photochemical processes, all of them involving cleavage of the tetrazolering: e.g. (1) molecular nitrogen loss, with production of 1-phenyl- diaziridin-3-one; this compound reacts subsequently to form 1-aza-1,2,4,6- cycloheptatetraene and isocyanic acid (eventually, also to form CO plus phenyldiazene); (2) cleavage of the C(5)–N(1) and N(3)–N(4) tetrazole-ring bonds, with production of phenylazide and isocyanic acid, with phenylazide then losingN2 to yield as final product 1-aza-1,2,4,6-cycloheptatetraene; and (3) cleavage of the N(1)–N(2) and N(4)–C(5) tetrazole-ring bonds, to yield phenylisocyanate and azide. The observed photochemical processes are distinct from the preferred thermal fragmentation channel, where CO is produced together with a weak IR absorbant species.
publishDate 2006
dc.date.none.fl_str_mv 2006-12
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/11336/116103
Gomez Zavaglia, Andrea; Reva, Igor D.; Frija, Luis M.T.; Cristiano, María Lurdes; Fausto, Rui; Photochemistry of 1-phenyl-tetrazolone isolated in solid argon; Elsevier Science Sa; Journal of Photochemistry and Photobiology A: Chemistry; 179; 3; 12-2006; 243-255
1010-6030
1873-2666
CONICET Digital
CONICET
url http://hdl.handle.net/11336/116103
identifier_str_mv Gomez Zavaglia, Andrea; Reva, Igor D.; Frija, Luis M.T.; Cristiano, María Lurdes; Fausto, Rui; Photochemistry of 1-phenyl-tetrazolone isolated in solid argon; Elsevier Science Sa; Journal of Photochemistry and Photobiology A: Chemistry; 179; 3; 12-2006; 243-255
1010-6030
1873-2666
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jphotochem.2005.08.021
info:eu-repo/semantics/altIdentifier/url/https://tinyurl.com/y5ep9ogb
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 Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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
_version_ 1842269694757699584
score 13.13397

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