Publication
Photochemical ring-opening and intramolecular hydrogen shift reactions in sulfur analogues of a-pyrone
dc.contributor.author | Breda, S. | |
dc.contributor.author | Reva, I. D. | |
dc.contributor.author | Lapinski, L. | |
dc.contributor.author | Cristiano, Maria Lurdes Santos | |
dc.contributor.author | Frija, L. | |
dc.contributor.author | Fausto, R. | |
dc.date.accessioned | 2014-06-09T14:45:27Z | |
dc.date.available | 2014-06-09T14:45:27Z | |
dc.date.issued | 2006 | |
dc.date.updated | 2014-06-05T10:09:37Z | |
dc.description.abstract | A 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.citation | Breda, 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.doi | http://dx.doi.org/10.1021/jp061139k | |
dc.identifier.issn | 1089-5639 | |
dc.identifier.other | AUT: MCR00716; | |
dc.identifier.uri | http://hdl.handle.net/10400.1/4261 | |
dc.language.iso | eng | por |
dc.peerreviewed | yes | por |
dc.publisher | American Chemical Society | por |
dc.title | Photochemical ring-opening and intramolecular hydrogen shift reactions in sulfur analogues of a-pyrone | por |
dc.type | journal article | |
dspace.entity.type | Publication | |
oaire.citation.endPage | 6425 | por |
oaire.citation.issue | 20 | por |
oaire.citation.startPage | 6415 | por |
oaire.citation.title | Journal of Physical Chemistry A | por |
oaire.citation.volume | 110 | por |
person.familyName | Cristiano | |
person.givenName | Maria de Lurdes | |
person.identifier.ciencia-id | E411-6006-5A01 | |
person.identifier.orcid | 0000-0002-9447-2855 | |
person.identifier.rid | G-2345-2012 | |
person.identifier.scopus-author-id | 9238724800 | |
rcaap.rights | restrictedAccess | por |
rcaap.type | article | por |
relation.isAuthorOfPublication | b16751a6-748e-44b0-9c59-058cbd5b2cc3 | |
relation.isAuthorOfPublication.latestForDiscovery | b16751a6-748e-44b0-9c59-058cbd5b2cc3 |
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