Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole
Autor(a) principal: | |
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Data de Publicação: | 2006 |
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/10316/5085 https://doi.org/10.1016/j.jphotochem.2005.10.012 |
Resumo: | The molecular structure, vibrational spectra and photochemistry of 5-methoxy-1-phenyl-1H-tetrazole (5MPT) were studied by matrix isolation infrared spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. According to the calculations, only one double degenerated-by-symmetry minimum exists in the ground state PES of the compound. In this structure, the dihedral angle between the two rings (phenyl and tetrazole) is ca. 30°, whereas the methoxyl group stays nearly in the plane of the tetrazole ring. In consonance with the theoretical predictions, only one molecular species was experimentally observed in the as-deposited argon matrices. Theoretical calculations were also used to help in assignment of the experimental spectrum of the compound, the calculated spectrum showing a very good agreement with the experimental data. In situ UV-irradiation ([lambda] > 235 nm) of the matrix-isolated 5MPT induced unimolecular decomposition of the compound, which led mainly to production of methylcyanate and phenylazide, this latter further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. 3-Methoxy-1-phenyl-1H-diazirene was also observed experimentally as minor product, resulting from direct elimination of molecular nitrogen from 5MPT. |
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Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole5-Methoxy-1-phenyl-1H-tetrazole3-Methoxy-1-phenyl-1H-diazirenePhenylazide1-Aza-1,2,4,6-cycloheptatetraeneMethylcyanateTetrazole ring cleavageMatrix isolation IR spectroscopyDFT(B3LYP)/6-311++G(d,p) calculationsThe molecular structure, vibrational spectra and photochemistry of 5-methoxy-1-phenyl-1H-tetrazole (5MPT) were studied by matrix isolation infrared spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. According to the calculations, only one double degenerated-by-symmetry minimum exists in the ground state PES of the compound. In this structure, the dihedral angle between the two rings (phenyl and tetrazole) is ca. 30°, whereas the methoxyl group stays nearly in the plane of the tetrazole ring. In consonance with the theoretical predictions, only one molecular species was experimentally observed in the as-deposited argon matrices. Theoretical calculations were also used to help in assignment of the experimental spectrum of the compound, the calculated spectrum showing a very good agreement with the experimental data. In situ UV-irradiation ([lambda] > 235 nm) of the matrix-isolated 5MPT induced unimolecular decomposition of the compound, which led mainly to production of methylcyanate and phenylazide, this latter further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. 3-Methoxy-1-phenyl-1H-diazirene was also observed experimentally as minor product, resulting from direct elimination of molecular nitrogen from 5MPT.http://www.sciencedirect.com/science/article/B6TGY-4HR72GH-1/1/90b3c1e44ce4d246bfcebbe8a3a7a52a2006info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleaplication/PDFhttp://hdl.handle.net/10316/5085http://hdl.handle.net/10316/5085https://doi.org/10.1016/j.jphotochem.2005.10.012engJournal of Photochemistry and Photobiology A: Chemistry. 180:1-2 (2006) 175-183Gómez-Zavaglia, AndreaReva, I. D.Frija, L.Cristiano, M. L. S.Fausto, R.info: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:RCAAP2021-09-03T10:14:00Zoai:estudogeral.uc.pt:10316/5085Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:32.310260Repositório 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 |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
title |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
spellingShingle |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole Gómez-Zavaglia, Andrea 5-Methoxy-1-phenyl-1H-tetrazole 3-Methoxy-1-phenyl-1H-diazirene Phenylazide 1-Aza-1,2,4,6-cycloheptatetraene Methylcyanate Tetrazole ring cleavage Matrix isolation IR spectroscopy DFT(B3LYP)/6-311++G(d,p) calculations |
title_short |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
title_full |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
title_fullStr |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
title_full_unstemmed |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
title_sort |
Infrared spectrum and UV-induced photochemistry of matrix-isolated 5-methoxy-1-phenyl-1H-tetrazole |
author |
Gómez-Zavaglia, Andrea |
author_facet |
Gómez-Zavaglia, Andrea Reva, I. D. Frija, L. Cristiano, M. L. S. Fausto, R. |
author_role |
author |
author2 |
Reva, I. D. Frija, L. Cristiano, M. L. S. Fausto, R. |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Gómez-Zavaglia, Andrea Reva, I. D. Frija, L. Cristiano, M. L. S. Fausto, R. |
dc.subject.por.fl_str_mv |
5-Methoxy-1-phenyl-1H-tetrazole 3-Methoxy-1-phenyl-1H-diazirene Phenylazide 1-Aza-1,2,4,6-cycloheptatetraene Methylcyanate Tetrazole ring cleavage Matrix isolation IR spectroscopy DFT(B3LYP)/6-311++G(d,p) calculations |
topic |
5-Methoxy-1-phenyl-1H-tetrazole 3-Methoxy-1-phenyl-1H-diazirene Phenylazide 1-Aza-1,2,4,6-cycloheptatetraene Methylcyanate Tetrazole ring cleavage Matrix isolation IR spectroscopy DFT(B3LYP)/6-311++G(d,p) calculations |
description |
The molecular structure, vibrational spectra and photochemistry of 5-methoxy-1-phenyl-1H-tetrazole (5MPT) were studied by matrix isolation infrared spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. According to the calculations, only one double degenerated-by-symmetry minimum exists in the ground state PES of the compound. In this structure, the dihedral angle between the two rings (phenyl and tetrazole) is ca. 30°, whereas the methoxyl group stays nearly in the plane of the tetrazole ring. In consonance with the theoretical predictions, only one molecular species was experimentally observed in the as-deposited argon matrices. Theoretical calculations were also used to help in assignment of the experimental spectrum of the compound, the calculated spectrum showing a very good agreement with the experimental data. In situ UV-irradiation ([lambda] > 235 nm) of the matrix-isolated 5MPT induced unimolecular decomposition of the compound, which led mainly to production of methylcyanate and phenylazide, this latter further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. 3-Methoxy-1-phenyl-1H-diazirene was also observed experimentally as minor product, resulting from direct elimination of molecular nitrogen from 5MPT. |
publishDate |
2006 |
dc.date.none.fl_str_mv |
2006 |
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/10316/5085 http://hdl.handle.net/10316/5085 https://doi.org/10.1016/j.jphotochem.2005.10.012 |
url |
http://hdl.handle.net/10316/5085 https://doi.org/10.1016/j.jphotochem.2005.10.012 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Journal of Photochemistry and Photobiology A: Chemistry. 180:1-2 (2006) 175-183 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
aplication/PDF |
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 |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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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 |
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