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...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2015 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/93253 |
| Acceso en línea: | http://hdl.handle.net/11336/93253 |
| Access Level: | acceso abierto |
| Palabra clave: | S-nitrosothiol Conformational analysis IR Spectroscopy Vibrational properties Molecular structure https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | 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. |
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