Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3

Autores
Rodriguez Pirani, Lucas Sebastian; Erben, Mauricio Federico; Willner, Helge; Romano, Rosana Mariel; Della Védova, Carlos Omar
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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.
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
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
Fil: Willner, Helge. Bergische Universitat Wuppertal; Alemania
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
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
Materia
Matrix-Isolation
Photochemistry
Ir Spectroscopy
Raman
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/24808
Acceder
id CONICETDig_f64b563b554a2ecd7fbeef7e7895dba6
oai_identifier_str oai:ri.conicet.gov.ar:11336/24808
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3Rodriguez Pirani, Lucas SebastianErben, Mauricio FedericoWillner, HelgeRomano, Rosana MarielDella Védova, Carlos OmarMatrix-IsolationPhotochemistryIr SpectroscopyRamanhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The 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.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"; ArgentinaFil: 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"; ArgentinaFil: Willner, Helge. Bergische Universitat Wuppertal; AlemaniaFil: 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"; ArgentinaFil: 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"; ArgentinaAmerican Chemical Society2014-11-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24808Rodriguez 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; 11193-112031089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp507863binfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp507863binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:52:16Zoai:ri.conicet.gov.ar:11336/24808instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:52:16.475CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
title Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
spellingShingle Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
Rodriguez Pirani, Lucas Sebastian
Matrix-Isolation
Photochemistry
Ir Spectroscopy
Raman
title_short Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
title_full Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
title_fullStr Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
title_full_unstemmed Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
title_sort Matrix Isolation Study of the Conformations and Photochemistry of S‑Ethyl Fluorothioformate, FC(O)SCH2CH3
dc.creator.none.fl_str_mv Rodriguez Pirani, Lucas Sebastian
Erben, Mauricio Federico
Willner, Helge
Romano, Rosana Mariel
Della Védova, Carlos Omar
author Rodriguez Pirani, Lucas Sebastian
author_facet Rodriguez Pirani, Lucas Sebastian
Erben, Mauricio Federico
Willner, Helge
Romano, Rosana Mariel
Della Védova, Carlos Omar
author_role author
author2 Erben, Mauricio Federico
Willner, Helge
Romano, Rosana Mariel
Della Védova, Carlos Omar
author2_role author
author
author
author
dc.subject.none.fl_str_mv Matrix-Isolation
Photochemistry
Ir Spectroscopy
Raman
topic Matrix-Isolation
Photochemistry
Ir Spectroscopy
Raman
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 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.
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
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
Fil: Willner, Helge. Bergische Universitat Wuppertal; Alemania
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
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
description 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.
publishDate 2014
dc.date.none.fl_str_mv 2014-11-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/24808
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
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24808
identifier_str_mv 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
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp507863b
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp507863b
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1842269147313995776
score 13.13397

Publicaciones similares