Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/17918
DC FieldValueLanguage
dc.contributor.authorBreda, S.-
dc.contributor.authorReva, I.-
dc.contributor.authorLapinski, L.-
dc.contributor.authorCristiano, M. L. S.-
dc.contributor.authorFrija, L.-
dc.contributor.authorFausto, R.-
dc.date.accessioned2011-12-14T15:51:58Z-
dc.date.available2011-12-14T15:51:58Z-
dc.date.issued2006-05-
dc.identifier.urihttp://hdl.handle.net/10316/17918-
dc.description.abstractA combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the photochemistry of sulfur analogues of α-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 (λ > 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 α-bond. Other photoprocesses, not involving the α-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 α-bond cleavage in a compound with a CS 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 α 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.language.isoengpor
dc.publisherAmerican Chemical Societypor
dc.rightsopenAccesspor
dc.titlePhotochemical Ring-Opening and Intramolecular Hydrogen Shift Reactions in Sulfur Analogues of α-Pyronepor
dc.typearticlepor
degois.publication.firstPage6415por
degois.publication.lastPage6425por
degois.publication.titleJ. Phys. Chem. Apor
dc.peerreviewedYespor
dc.identifier.doi10.1021/jp061139k-
degois.publication.volume110por
uc.controloAutoridadeSim-
item.fulltextCom Texto completo-
item.languageiso639-1en-
item.grantfulltextopen-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.orcid0000-0001-5983-7743-
crisitem.author.orcid0000-0002-8264-6854-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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