Artículo
Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
Fecha de publicación:
06/2024
Editorial:
MDPI
Revista:
Spectroscopy Journal
ISSN:
2813-446X
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
The conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through experimental vibrational methods (gas-phase FTIR, liquid-phase Raman, and Ar matrix FTIR spectroscopy) and density functional theory (DFT) calculations. A potential energy surface was computed using the B3P86/6-31+g(d) approximation as a function of the dihedral angles τ1 = CC−OS and τ2 = CO−SC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp, and cc-pvtz). The global minimum corresponds to a syn–anti conformer (the C=O double-bound syn with respect the O−S single bond and the C−O single bond anti with respect to S−C single bond). The other two minima represent enantiomeric syn–gauche forms. The Ar matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broadband UV–visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperature was composed of approximately 60–70% of the syn–anti conformer and 30–40% of the syn–gauche form.
Palabras clave:
conformations
,
matrix FTIR
,
gas-phase FTIR
,
Raman
,
DFT
Archivos asociados
Licencia
Identificadores
Colecciones
Articulos(CCT - LA PLATA)
Articulos de CTRO.CIENTIFICO TECNOL.CONICET - LA PLATA
Articulos de CTRO.CIENTIFICO TECNOL.CONICET - LA PLATA
Articulos(CEQUINOR)
Articulos de CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Articulos de CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Citación
Spaltro, Agustín; Pelúas, Melina Gisella; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation; MDPI; Spectroscopy Journal; 2; 2; 6-2024; 68-81
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