Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)

Autores
Canneva, Antonela; Della Védova, Carlos Omar; Mitzel, Norbert W.; Erben, Mauricio Federico
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The simple 2,2,2-trifluoroethyl thionitrite molecule, CF3CH2SNO, has been prepared in good yield for the first time using CF3CH2SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF3CH2SNO follows, in the temperature range between 226 and 268 K, the equation log p = 12.0-3881/T (p/bar, T/K), and its extrapolated boiling point reaches 51 °C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH3CH2SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2(full) level of theory with extended basis sets [6-311+G(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (N=O double bond syn with respect to the C-S single bond) has been estimated to be ca. 79 and 75% for CF3CH2SNO and CH3CH2SNO, respectively.
Fil: Canneva, Antonela. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; Argentina
Fil: Della Védova, Carlos Omar. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; Argentina
Fil: Mitzel, Norbert W.. Universitat Bielefeld; Alemania
Fil: Erben, Mauricio Federico. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; Argentina
Materia
S-nitrosothiol
Conformational analysis
IR Spectroscopy
Vibrational properties
Molecular structure
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/93253
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/93253
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)Canneva, AntonelaDella Védova, Carlos OmarMitzel, Norbert W.Erben, Mauricio FedericoS-nitrosothiolConformational analysisIR SpectroscopyVibrational propertiesMolecular structurehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The simple 2,2,2-trifluoroethyl thionitrite molecule, CF3CH2SNO, has been prepared in good yield for the first time using CF3CH2SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF3CH2SNO follows, in the temperature range between 226 and 268 K, the equation log p = 12.0-3881/T (p/bar, T/K), and its extrapolated boiling point reaches 51 °C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH3CH2SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2(full) level of theory with extended basis sets [6-311+G(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (N=O double bond syn with respect to the C-S single bond) has been estimated to be ca. 79 and 75% for CF3CH2SNO and CH3CH2SNO, respectively.Fil: Canneva, Antonela. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; ArgentinaFil: Della Védova, Carlos Omar. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; ArgentinaFil: Mitzel, Norbert W.. Universitat Bielefeld; AlemaniaFil: Erben, Mauricio Federico. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; ArgentinaAmerican Chemical Society2015-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/93253Canneva, Antonela; Della Védova, Carlos Omar; Mitzel, Norbert W.; Erben, Mauricio Federico; Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F); American Chemical Society; Journal of Physical Chemistry A; 119; 9; 3-2015; 1524-15331089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp507406winfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp507406winfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:59:15Zoai:ri.conicet.gov.ar:11336/93253instacron: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 09:59:16.083CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
title Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
spellingShingle Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
Canneva, Antonela
S-nitrosothiol
Conformational analysis
IR Spectroscopy
Vibrational properties
Molecular structure
title_short Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
title_full Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
title_fullStr Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
title_full_unstemmed Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
title_sort Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
dc.creator.none.fl_str_mv Canneva, Antonela
Della Védova, Carlos Omar
Mitzel, Norbert W.
Erben, Mauricio Federico
author Canneva, Antonela
author_facet Canneva, Antonela
Della Védova, Carlos Omar
Mitzel, Norbert W.
Erben, Mauricio Federico
author_role author
author2 Della Védova, Carlos Omar
Mitzel, Norbert W.
Erben, Mauricio Federico
author2_role author
author
author
dc.subject.none.fl_str_mv S-nitrosothiol
Conformational analysis
IR Spectroscopy
Vibrational properties
Molecular structure
topic S-nitrosothiol
Conformational analysis
IR Spectroscopy
Vibrational properties
Molecular structure
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 simple 2,2,2-trifluoroethyl thionitrite molecule, CF3CH2SNO, has been prepared in good yield for the first time using CF3CH2SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF3CH2SNO follows, in the temperature range between 226 and 268 K, the equation log p = 12.0-3881/T (p/bar, T/K), and its extrapolated boiling point reaches 51 °C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH3CH2SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2(full) level of theory with extended basis sets [6-311+G(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (N=O double bond syn with respect to the C-S single bond) has been estimated to be ca. 79 and 75% for CF3CH2SNO and CH3CH2SNO, respectively.
Fil: Canneva, Antonela. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; Argentina
Fil: Della Védova, Carlos Omar. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; Argentina
Fil: Mitzel, Norbert W.. Universitat Bielefeld; Alemania
Fil: Erben, Mauricio Federico. Facultad de Ciencias Exactas, Universidad Nacional de la Plata; Argentina
description The simple 2,2,2-trifluoroethyl thionitrite molecule, CF3CH2SNO, has been prepared in good yield for the first time using CF3CH2SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF3CH2SNO follows, in the temperature range between 226 and 268 K, the equation log p = 12.0-3881/T (p/bar, T/K), and its extrapolated boiling point reaches 51 °C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH3CH2SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2(full) level of theory with extended basis sets [6-311+G(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (N=O double bond syn with respect to the C-S single bond) has been estimated to be ca. 79 and 75% for CF3CH2SNO and CH3CH2SNO, respectively.
publishDate 2015
dc.date.none.fl_str_mv 2015-03
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/11336/93253
Canneva, Antonela; Della Védova, Carlos Omar; Mitzel, Norbert W.; Erben, Mauricio Federico; Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F); American Chemical Society; Journal of Physical Chemistry A; 119; 9; 3-2015; 1524-1533
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/93253
identifier_str_mv Canneva, Antonela; Della Védova, Carlos Omar; Mitzel, Norbert W.; Erben, Mauricio Federico; Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F); American Chemical Society; Journal of Physical Chemistry A; 119; 9; 3-2015; 1524-1533
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/url/http://pubs.acs.org/doi/abs/10.1021/jp507406w
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp507406w
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv 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
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score 13.13397

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