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Photochemical ring-opening and intramolecular hydrogen shift reactions in sulfur analogues of a-pyrone

2006Journal article Restricted access
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dc.contributor.authorBreda, S.
dc.contributor.authorReva, I. D.
dc.contributor.authorLapinski, L.
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.contributor.authorFrija, L.
dc.contributor.authorFausto, R.
dc.date.accessioned2014-06-09T14:45:27Z
dc.date.available2014-06-09T14:45:27Z
dc.date.issued2006
dc.date.updated2014-06-05T10:09:37Z
dc.description.abstractA combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the photochemistry of sulfur analogues of R-pyrone [2H-thiopyran-2-one (TP) and 2H-pyran-2-thione (PT)] was carried out. The vibrational spectra of monomers of the compounds isolated in low-temperature argon matrixes were studied experimentally and assigned completely on the basis of theoretical calculations. UV irradiation (ì > 337 nm) of the studied compounds isolated in low-temperature matrixes results mainly in the ring-opening reaction by means of the cleavage of the R-bond. Other photoprocesses, not involving the R-bond-cleavage step (such as generation of Dewar valence isomer), correspond to the minor reaction channels in both studied compounds. The ring-opening photoreaction in PT represents the first reported case of an R-bond cleavage in a compound with a CdS group attached to a six-membered ring, in which the internal strain practically does not exist, whereas the corresponding reaction in TP (a cleavage of a C-S bond in the R position with respect to a carbonyl group) is now reported for the first time. Following the ring-opening reactions, isomerization processes and intramolecular hydrogen shift reactions were observed, enabling production of TP from PT and vice versa. A detailed study of such processes was undertaken, and kinetical and mechanistical data are presented and discussed.por
dc.identifier.citationBreda, S.; Reva, I.; Lapinski, L.; Cristiano, M. L. S.; Frija, L.; Fausto, R. Photochemical Ring-Opening and Intramolecular Hydrogen Shift Reactions in Sulfur Analogues of a-Pyrone, The Journal of Physical Chemistry A, 110, 20, 6415-6425, 2006.por
dc.identifier.doihttp://dx.doi.org/10.1021/jp061139k
dc.identifier.issn1089-5639
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4261
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherAmerican Chemical Societypor
dc.titlePhotochemical ring-opening and intramolecular hydrogen shift reactions in sulfur analogues of a-pyronepor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage6425por
oaire.citation.issue20por
oaire.citation.startPage6415por
oaire.citation.titleJournal of Physical Chemistry Apor
oaire.citation.volume110por
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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