Mostrar el registro sencillo del ítem
dc.contributor.author
Rodriguez Pirani, Lucas Sebastian
dc.contributor.author
Erben, Mauricio Federico
dc.contributor.author
Willner, Helge
dc.contributor.author
Romano, Rosana Mariel
dc.contributor.author
Della Védova, Carlos Omar
dc.date.available
2017-09-21T17:09:21Z
dc.date.issued
2014-11-03
dc.identifier.citation
Rodriguez Pirani, Lucas Sebastian; Erben, Mauricio Federico; Willner, Helge; Romano, Rosana Mariel; Della Védova, Carlos Omar; Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3; American Chemical Society; Journal of Physical Chemistry A; 118; 3-11-2014; 11193-11203
dc.identifier.issn
1089-5639
dc.identifier.uri
http://hdl.handle.net/11336/24808
dc.description.abstract
The IR spectra of S-ethyl fluorothioformate, FC(O)SCH2CH3, were recorded in the vapor phase and compared with the Raman spectrum in the liquid state. Additional IR spectra of the compound isolated in argon and nitrogen matrices at ca. 12 K were also recorded. The title compound exhibits rich conformational equilibria at room temperature being C1 the most stable symmetry with a synperiplanar orientation of the carbonyl double bond (C O) with respect to the S−C(sp3 ) single bond, while the C−C bond of the ethyl group presents a gauche orientation with respect to the C−S single bond. Several bands assigned to a second conformer were also observed in the IR matrix spectra. This second rotamer presents a planar skeleton (Cs point group) retaining the prevalent syn orientation of the FC(O)SCH2CH3 molecule with an antiperiplanar orientation of the C−C bond of the ethyl group with respect to the C−S bond. The variation of the nozzle temperature before matrix gas deposition gives rise to different conformer ratios. With these data an enthalpy difference of 0.45 kcal mol−1 can be calculated between the more stable C1 and the Cs conformers. A third form, corresponding to the anti-gauche conformer, is also detected when the matrix is exposed to broad-band UV−visible irradiation. Moreover, the photochemistry of the Ar and N2 matrix-isolated species is studied. Conformational interconversion is observed at short irradiation times, whereas a decarbonylation process with the concomitant formation of a HC(S)CH3:HF molecular complex dominates the photochemistry of FC(O)SCH2CH3 of longer irradiation times. The new ethyl fluoro sulfide, FSCH2CH3, is proposed as an intermediate species.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Matrix-Isolation
dc.subject
Photochemistry
dc.subject
Ir Spectroscopy
dc.subject
Raman
dc.subject.classification
Otras Ciencias Químicas
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-09-18T14:33:48Z
dc.journal.volume
118
dc.journal.pagination
11193-11203
dc.journal.pais
Estados Unidos
dc.journal.ciudad
Washington
dc.description.fil
Fil: Rodriguez Pirani, Lucas Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
dc.description.fil
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
dc.description.fil
Fil: Willner, Helge. Bergische Universitat Wuppertal; Alemania
dc.description.fil
Fil: Romano, Rosana Mariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
dc.description.fil
Fil: Della Védova, Carlos Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
dc.journal.title
Journal of Physical Chemistry A
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/jp507863b
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp507863b
Archivos asociados