Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole
Autor(a) principal: | |
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Data de Publicação: | 2002 |
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/10316/10721 https://doi.org/10.1039/b111329c |
Resumo: | The vibrational spectra of 5-chlorotetrazole (CN4HCl) isolated in an argon matrix (T=8.5 K) and in the solid state (at room temperature) were studied. The infrared spectrum of monomers of 5-chlorotetrazole isolated in an argon matrix agrees well with the spectrum predicted theoretically (DFT(B3LYP)/6-31G*) for the 2H-tautomer of the compound. The bands assigned to the 1H-tautomer appear in the experimental spectrum as very low intensity features. Based on the relative intensities of the bands in the spectra of the 1H- and 2H- tautomers, the relative amount of the first tautomer in this matrix can be estimated as 1%. Three matrixes were deposited with different nozzle temperatures and the enthalpy difference between the tautomers H=8.0 kJ mol–1 was estimated using the Van't Hoff relation. The internal energy difference between the two tautomers was predicted theoretically (DFT B3LYP/6-31G*) as 12.6 kJ mol–1. This is in reasonable agreement with experimental observations. In the crystalline phase, this compound exists in its 1H-tautomeric form. Accordingly, the IR spectrum of polycrystalline 5-chlorotetrazole is well reproduced by the spectrum predicted theoretically for the 1H- tautomer. |
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Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazoleThe vibrational spectra of 5-chlorotetrazole (CN4HCl) isolated in an argon matrix (T=8.5 K) and in the solid state (at room temperature) were studied. The infrared spectrum of monomers of 5-chlorotetrazole isolated in an argon matrix agrees well with the spectrum predicted theoretically (DFT(B3LYP)/6-31G*) for the 2H-tautomer of the compound. The bands assigned to the 1H-tautomer appear in the experimental spectrum as very low intensity features. Based on the relative intensities of the bands in the spectra of the 1H- and 2H- tautomers, the relative amount of the first tautomer in this matrix can be estimated as 1%. Three matrixes were deposited with different nozzle temperatures and the enthalpy difference between the tautomers H=8.0 kJ mol–1 was estimated using the Van't Hoff relation. The internal energy difference between the two tautomers was predicted theoretically (DFT B3LYP/6-31G*) as 12.6 kJ mol–1. This is in reasonable agreement with experimental observations. In the crystalline phase, this compound exists in its 1H-tautomeric form. Accordingly, the IR spectrum of polycrystalline 5-chlorotetrazole is well reproduced by the spectrum predicted theoretically for the 1H- tautomer.Fundação para a Ciência e Tecnologia, projecto de investigação PRAXIS/P/QUI/10137/1998).Royal Society of Chemistry2002-04-15info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10721http://hdl.handle.net/10316/10721https://doi.org/10.1039/b111329cengPhysical Chemistry Chemical Physics. 4 (2002) 1725-17311463-9076Bugalho, Susana C. S.Serra, A. C.Lapinski, LeszekCristiano, M. Lurdes S.Fausto, 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:RCAAP2020-05-29T10:05:32Zoai:estudogeral.uc.pt:10316/10721Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:37.092191Repositório 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 |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
title |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
spellingShingle |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole Bugalho, Susana C. S. |
title_short |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
title_full |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
title_fullStr |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
title_full_unstemmed |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
title_sort |
Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole |
author |
Bugalho, Susana C. S. |
author_facet |
Bugalho, Susana C. S. Serra, A. C. Lapinski, Leszek Cristiano, M. Lurdes S. Fausto, Rui |
author_role |
author |
author2 |
Serra, A. C. Lapinski, Leszek Cristiano, M. Lurdes S. Fausto, Rui |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Bugalho, Susana C. S. Serra, A. C. Lapinski, Leszek Cristiano, M. Lurdes S. Fausto, Rui |
description |
The vibrational spectra of 5-chlorotetrazole (CN4HCl) isolated in an argon matrix (T=8.5 K) and in the solid state (at room temperature) were studied. The infrared spectrum of monomers of 5-chlorotetrazole isolated in an argon matrix agrees well with the spectrum predicted theoretically (DFT(B3LYP)/6-31G*) for the 2H-tautomer of the compound. The bands assigned to the 1H-tautomer appear in the experimental spectrum as very low intensity features. Based on the relative intensities of the bands in the spectra of the 1H- and 2H- tautomers, the relative amount of the first tautomer in this matrix can be estimated as 1%. Three matrixes were deposited with different nozzle temperatures and the enthalpy difference between the tautomers H=8.0 kJ mol–1 was estimated using the Van't Hoff relation. The internal energy difference between the two tautomers was predicted theoretically (DFT B3LYP/6-31G*) as 12.6 kJ mol–1. This is in reasonable agreement with experimental observations. In the crystalline phase, this compound exists in its 1H-tautomeric form. Accordingly, the IR spectrum of polycrystalline 5-chlorotetrazole is well reproduced by the spectrum predicted theoretically for the 1H- tautomer. |
publishDate |
2002 |
dc.date.none.fl_str_mv |
2002-04-15 |
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/10316/10721 http://hdl.handle.net/10316/10721 https://doi.org/10.1039/b111329c |
url |
http://hdl.handle.net/10316/10721 https://doi.org/10.1039/b111329c |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Physical Chemistry Chemical Physics. 4 (2002) 1725-1731 1463-9076 |
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 |
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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) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799133906965889024 |