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

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...

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Detalles Bibliográficos
Autores principales: Cánneva, Antonela, Della Védova, Carlos Omar, Mitzel, Norbert W., Erben, Mauricio Federico
Formato: Articulo Preprint
Lenguaje:Inglés
Publicado: 2015
Materias:
Química
S-nitrosothiol
Conformational analysis
IR spectroscopy
Vibrational properties
Molecular structure
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/98562
https://ri.conicet.gov.ar/11336/93253
http://pubs.acs.org/doi/abs/10.1021/jp507406w
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-98562
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
S-nitrosothiol
Conformational analysis
IR spectroscopy
Vibrational properties
Molecular structure
spellingShingle Química
S-nitrosothiol
Conformational analysis
IR spectroscopy
Vibrational properties
Molecular structure
Cánneva, 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)
topic_facet Química
S-nitrosothiol
Conformational analysis
IR spectroscopy
Vibrational properties
Molecular structure
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.
format Articulo
Preprint
author Cánneva, Antonela
Della Védova, Carlos Omar
Mitzel, Norbert W.
Erben, Mauricio Federico
author_facet Cánneva, Antonela
Della Védova, Carlos Omar
Mitzel, Norbert W.
Erben, Mauricio Federico
author_sort Cánneva, Antonela
title Conformational properties of ethyl- and 2,2,2-trifluoroethyl thionitrites, (CX3CH2SNO, X = H and F)
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)
publishDate 2015
url http://sedici.unlp.edu.ar/handle/10915/98562
https://ri.conicet.gov.ar/11336/93253
http://pubs.acs.org/doi/abs/10.1021/jp507406w
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