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Structure and photochemistry of a novel tetrazole-saccharyl conjugate isolated in solid argon

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dc.contributor.authorIsmael, Amin
dc.contributor.authorBorba, A.
dc.contributor.authorDuarte, L.
dc.contributor.authorGiuliano, B. M.
dc.contributor.authorGómez-Zavaglia, A.
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.date.accessioned2014-06-17T10:56:09Z
dc.date.available2014-06-17T10:56:09Z
dc.date.issued2012
dc.date.updated2014-06-12T08:54:23Z
dc.description.abstractA combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(3df,3pd) study of the novel synthesised tetrazole-saccharyl conjugate 2-[1-(1H-tetrazol-5-yl)ethyl]-1,2-benzisothiazol-3(2H)-one 1,1-dioxide [1-TE-BZT] was performed. In the gas phase, at room temperature, the compound exists as a mixture of six isomeric forms (four conformers of 1H tautomer and two conformers of 2H tautomer). According to theoretical calculations, conformers 1H were the most stable and the relative energies among the three most stable forms are lower than 4 kJ mol 1. These conformers benefit from stabilising intramolecular hydrogen bonds-like interactions involving the 1H of the tetrazole ring and the carbonyl oxygen of the saccharyl moiety. The photochemistry of 1-TE-BZT in solid argon was investigated and theoretical DFT/B3LYP/6-311++G(3df,3pd) calculations also helped in assignment of the experimental bands. A quick consumption of the compound occurred after irradiation of the matrix with UV laser light at k = 275 nm. Three photofragmentation pathways were proposed, one leading to 2-[1-(1H-diaziren-3-yl)ethyl]-1,2-benzisothiazol-3(2H)-one 1,1-dioxide and molecular nitrogen, a second one giving 2-(1,1-dioxide-3-oxo-1,2-benzisothiazol-2(3H)-yl)propanenitrile and azide, and a third one involving loss of azide from the tetrazole ring and decarbonylation of the saccharyl ring of 1-TE-BZT to give acrylonitrile and 7-thia-8- azabicyclo[4.2.0] octa-1,3,5-triene 7,7 dioxide. The comparison of the relative intensities of the bands of the photoproducts obtained from the three channels allowed us to consider the latter pathway, involving an unprecedented photocleavage of the benzisothiazole (saccharyl) ring, as the preferred photodegradation channel of 1-TE-BZT.por
dc.identifier.citationIsmael, A.; Borba, A.; Duarte, L.; Giuliano, B.M.; Gómez-Zavaglia, A.; Cristiano, M.L.S. Structure and photochemistry of a novel tetrazole-saccharyl conjugate isolated in solid argon, Journal of Molecular Structure, 1025, 1, 105-116, 2012.por
dc.identifier.doihttp://dx.doi.org/10.1016/j.molstruc.2012.04.081
dc.identifier.issn0022-2860
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4331
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherElsevierpor
dc.subjectSaccharinpor
dc.subjectTetrazolepor
dc.subjectMolecular structurepor
dc.subjectMatrix isolationpor
dc.subjectPhotochemistrypor
dc.titleStructure and photochemistry of a novel tetrazole-saccharyl conjugate isolated in solid argonpor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage116por
oaire.citation.issue1por
oaire.citation.startPage105por
oaire.citation.titleJournal of Molecular Structurepor
oaire.citation.volume1025por
person.familyNameIsmael
person.familyNameCristiano
person.givenNameAmin
person.givenNameMaria de Lurdes
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-7346-5998
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridA-8153-2013
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id35203489500
person.identifier.scopus-author-id9238724800
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationfa01ef7f-7a2a-4f74-a405-714360b862f3
relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryb16751a6-748e-44b0-9c59-058cbd5b2cc3

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