Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability
Autor(a) principal: | |
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Data de Publicação: | 2020 |
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/10316/91153 https://doi.org/10.1515/pac-2019-0402 |
Resumo: | The properties and applications of 2-methyl-(2H)-tetrazole-5-amino-saccharinate (2MTS) in catalysis and chelant-based chemotherapy stimulated investigations on its photostability. The photochemistry of monomeric 2MTS in solid argon (15 K) was compared with those of 2-methyl-(2H)-tetrazole-5-amine (2MT) and 1-methyl-(2H)-tetrazole-5-amine (1MT). Compounds were subjected to in situ narrowband UV-irradiation at different wavelengths. Reactions were followed by infrared spectroscopy, supported by B3LYP/6-311++G(d,p) calculations. Photochemical pathways for 2MT and 2MTS proved similar but photodegradation of 2MTS was 20× slower, unraveling the photostabilizing effect of the saccharyl moiety that extends into the nitrilimine formed from 2MTS and its antiaromatic 1H-diazirene isomer, which proved photostable at 290 nm, unlike the 1H-diazirene formed from 2MT. Analysis of the photochemistries of 2MTS/2MT (250 nm) and 1MT (222 nm), including energy trends calculated for the isomeric C2H5N3 species postulated/observed from photolysis and EPR results, enabled a deeper insight into the photodegradation mechanisms of 1,5-substituted and 2,5-substituted tetrazoles. We postulate a pivotal singlet state imidoylnitrene species, sN1, as common intermediate, which undergoes a Wolff-type isomerization to a stable carbodiimide. Photo-extrusion of N2 from 1,5-substituted tetrazoles generates sN1 directly but from 2,5-substituted tetrazoles it originates a nitrilimine, then a diazirene, which finally leads to sN1. Selective formation of cyanamide from 1MT requires photoisomerization between sN1 and sN2, accessible at 222 nm. EPR studies enabled the detection of methyl nitrene, arising from photolysis of 1H-diazirene intermediate. |
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Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability5-aminotetrazolesICPOC-24Light-induced selectivityPhotocleavage mechanismsReactive intermediatesSubstituent effectsTetrazole-saccharinatesThe properties and applications of 2-methyl-(2H)-tetrazole-5-amino-saccharinate (2MTS) in catalysis and chelant-based chemotherapy stimulated investigations on its photostability. The photochemistry of monomeric 2MTS in solid argon (15 K) was compared with those of 2-methyl-(2H)-tetrazole-5-amine (2MT) and 1-methyl-(2H)-tetrazole-5-amine (1MT). Compounds were subjected to in situ narrowband UV-irradiation at different wavelengths. Reactions were followed by infrared spectroscopy, supported by B3LYP/6-311++G(d,p) calculations. Photochemical pathways for 2MT and 2MTS proved similar but photodegradation of 2MTS was 20× slower, unraveling the photostabilizing effect of the saccharyl moiety that extends into the nitrilimine formed from 2MTS and its antiaromatic 1H-diazirene isomer, which proved photostable at 290 nm, unlike the 1H-diazirene formed from 2MT. Analysis of the photochemistries of 2MTS/2MT (250 nm) and 1MT (222 nm), including energy trends calculated for the isomeric C2H5N3 species postulated/observed from photolysis and EPR results, enabled a deeper insight into the photodegradation mechanisms of 1,5-substituted and 2,5-substituted tetrazoles. We postulate a pivotal singlet state imidoylnitrene species, sN1, as common intermediate, which undergoes a Wolff-type isomerization to a stable carbodiimide. Photo-extrusion of N2 from 1,5-substituted tetrazoles generates sN1 directly but from 2,5-substituted tetrazoles it originates a nitrilimine, then a diazirene, which finally leads to sN1. Selective formation of cyanamide from 1MT requires photoisomerization between sN1 and sN2, accessible at 222 nm. EPR studies enabled the detection of methyl nitrene, arising from photolysis of 1H-diazirene intermediate.De Gruyter2020info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/91153http://hdl.handle.net/10316/91153https://doi.org/10.1515/pac-2019-0402eng1365-30750033-4545https://www.degruyter.com/view/journals/pac/92/1/article-p49.xmlIsmael, AminAbe, ManabuLourenço, Rui Fausto Martins Ribeiro da SilvaCristiano, Maria L. S.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:RCAAP2022-05-25T06:12:11Zoai:estudogeral.uc.pt:10316/91153Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:11:05.914251Repositório 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 |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
title |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
spellingShingle |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability Ismael, Amin 5-aminotetrazoles ICPOC-24 Light-induced selectivity Photocleavage mechanisms Reactive intermediates Substituent effects Tetrazole-saccharinates |
title_short |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
title_full |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
title_fullStr |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
title_full_unstemmed |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
title_sort |
Insights into the photochemistry of 5-aminotetrazole derivatives with applications in coordination chemistry. Effect of the saccharyl moiety on the photostability |
author |
Ismael, Amin |
author_facet |
Ismael, Amin Abe, Manabu Lourenço, Rui Fausto Martins Ribeiro da Silva Cristiano, Maria L. S. |
author_role |
author |
author2 |
Abe, Manabu Lourenço, Rui Fausto Martins Ribeiro da Silva Cristiano, Maria L. S. |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Ismael, Amin Abe, Manabu Lourenço, Rui Fausto Martins Ribeiro da Silva Cristiano, Maria L. S. |
dc.subject.por.fl_str_mv |
5-aminotetrazoles ICPOC-24 Light-induced selectivity Photocleavage mechanisms Reactive intermediates Substituent effects Tetrazole-saccharinates |
topic |
5-aminotetrazoles ICPOC-24 Light-induced selectivity Photocleavage mechanisms Reactive intermediates Substituent effects Tetrazole-saccharinates |
description |
The properties and applications of 2-methyl-(2H)-tetrazole-5-amino-saccharinate (2MTS) in catalysis and chelant-based chemotherapy stimulated investigations on its photostability. The photochemistry of monomeric 2MTS in solid argon (15 K) was compared with those of 2-methyl-(2H)-tetrazole-5-amine (2MT) and 1-methyl-(2H)-tetrazole-5-amine (1MT). Compounds were subjected to in situ narrowband UV-irradiation at different wavelengths. Reactions were followed by infrared spectroscopy, supported by B3LYP/6-311++G(d,p) calculations. Photochemical pathways for 2MT and 2MTS proved similar but photodegradation of 2MTS was 20× slower, unraveling the photostabilizing effect of the saccharyl moiety that extends into the nitrilimine formed from 2MTS and its antiaromatic 1H-diazirene isomer, which proved photostable at 290 nm, unlike the 1H-diazirene formed from 2MT. Analysis of the photochemistries of 2MTS/2MT (250 nm) and 1MT (222 nm), including energy trends calculated for the isomeric C2H5N3 species postulated/observed from photolysis and EPR results, enabled a deeper insight into the photodegradation mechanisms of 1,5-substituted and 2,5-substituted tetrazoles. We postulate a pivotal singlet state imidoylnitrene species, sN1, as common intermediate, which undergoes a Wolff-type isomerization to a stable carbodiimide. Photo-extrusion of N2 from 1,5-substituted tetrazoles generates sN1 directly but from 2,5-substituted tetrazoles it originates a nitrilimine, then a diazirene, which finally leads to sN1. Selective formation of cyanamide from 1MT requires photoisomerization between sN1 and sN2, accessible at 222 nm. EPR studies enabled the detection of methyl nitrene, arising from photolysis of 1H-diazirene intermediate. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020 |
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/10316/91153 http://hdl.handle.net/10316/91153 https://doi.org/10.1515/pac-2019-0402 |
url |
http://hdl.handle.net/10316/91153 https://doi.org/10.1515/pac-2019-0402 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1365-3075 0033-4545 https://www.degruyter.com/view/journals/pac/92/1/article-p49.xml |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
De Gruyter |
publisher.none.fl_str_mv |
De Gruyter |
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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