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Photochemistry and vibrational vpectra of matrix-isolated 5-ethoxy-1-phenyl-1 H -tetrazole

2007Journal article Restricted access
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dc.contributor.authorFrija, L.
dc.contributor.authorReva, I. D.
dc.contributor.authorGómez-Zavaglia, A.
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.contributor.authorFausto, R.
dc.date.accessioned2014-06-09T12:26:21Z
dc.date.available2014-06-09T12:26:21Z
dc.date.issued2007
dc.date.updated2014-06-05T10:24:39Z
dc.description.abstractA combined matrix isolation FT-IR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the molecular structure and photochemistry of 5-ethoxy-1-phenyl-1H-tetrazole (5EPT) was performed. A new method of synthesis of the compound is described. Calculations show three minima, very close in energy and separated by low-energy barriers (less than 4 kJ mol-1), in the ground-state potential energy profile of the molecule. The method of matrix isolation enabled the reduction of the number of populated conformational states in the experiment at low temperature due to the effect known as conformational cooling. As a result, the spectrum of the as-deposited matrix of 5EPT closely matches that of the most stable conformer predicted theoretically, pointing to the existence of only this conformer in the low-temperature matrixes. In this structure, the dihedral angle between the two rings, phenyl and tetrazole, is ca. 30°, whereas the ethyl group stays nearly in the plane of the tetrazole ring and is as far as possible from the phenyl group. In situ UV irradiation (ì > 235 nm) of the matrix-isolated 5EPT induced unimolecular decomposition, which led mainly to production of ethylcyanate and phenylazide, this later compound further reacting to yield, as final product, 1-aza-1,2,4,6- cycloheptatetraene. Anti-aromatic 3-ethoxy-1-phenyl-1H-diazirene was also observed experimentally as minor photoproduct, resulting from direct extrusion of molecular nitrogen from 5EPT. This species has not been described before and is now characterized by infrared spectroscopy for the first time.por
dc.identifier.citationFrija, Luís M. T.; Reva, I. D.; Gómez-Zavaglia, A.; Cristiano, M. L. S.; Fausto, R. Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1 H -Tetrazole , The Journal of Physical Chemistry A, 111, 15, 2879-2888, 2007.por
dc.identifier.doihttp://dx.doi.org/10.1021/jp068556h
dc.identifier.issn1089-5639
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4251
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherAmerican Chemical Societypor
dc.titlePhotochemistry and vibrational vpectra of matrix-isolated 5-ethoxy-1-phenyl-1 H -tetrazolepor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage2888por
oaire.citation.issue15por
oaire.citation.startPage2879por
oaire.citation.titleJournal of Physical Chemistry Apor
oaire.citation.volume222por
person.familyNameCristiano
person.givenNameMaria de Lurdes
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id9238724800
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryb16751a6-748e-44b0-9c59-058cbd5b2cc3

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