S-(fluoroformyl)O-(trifluoroacetyl) Thioperoxide, FC(O)SOC(O)CF3: Gas Phase Structure and Conformational Properties.

SONIA ELIZABETH ULIC; KOSMA, A.; DELLA VEDOVA, CO; H OBERHAMMER,

JOURNAL OF PHYSICAL CHEMISTRY A

Año: 2006 vol. 110 p. 10201 - 10205

1089-5639

The geometric structure and conformational properties of S-(fluoroformyl)O-(trifluoroacetyl) thioperoxide, FC(O)S-OC(O)CF3, were investigated by gas electron diffraction, matrix isolation infrared spectroscopy, and quantum chemical calculations (B3LYP with the 6-31G* and aug-cc-pVTZ basis sets and MP2 with the 6-31G* basis set). The experimental methods result in a mixture of two conformers with gauche conformation around the S-O bond. In the main conformer (82(7)% according to GED at 298 K), the CdO bond of the FC(O) group is oriented syn with respect to the S-O bond and -(C-S-O-C) ) 75(3)°. In the minor conformer (18(7)%), this CdO is oriented anti. Both conformers possess syn orientation of the CdO bond of the CF3C(O) group. The conformational properties and geometric parameters are reproduced reasonably well by the quantum chemical calculations, except for the S-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).-OC(O)CF3, were investigated by gas electron diffraction, matrix isolation infrared spectroscopy, and quantum chemical calculations (B3LYP with the 6-31G* and aug-cc-pVTZ basis sets and MP2 with the 6-31G* basis set). The experimental methods result in a mixture of two conformers with gauche conformation around the S-O bond. In the main conformer (82(7)% according to GED at 298 K), the CdO bond of the FC(O) group is oriented syn with respect to the S-O bond and -(C-S-O-C) ) 75(3)°. In the minor conformer (18(7)%), this CdO is oriented anti. Both conformers possess syn orientation of the CdO bond of the CF3C(O) group. The conformational properties and geometric parameters are reproduced reasonably well by the quantum chemical calculations, except for the S-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).-O bond. In the main conformer (82(7)% according to GED at 298 K), the CdO bond of the FC(O) group is oriented syn with respect to the S-O bond and -(C-S-O-C) ) 75(3)°. In the minor conformer (18(7)%), this CdO is oriented anti. Both conformers possess syn orientation of the CdO bond of the CF3C(O) group. The conformational properties and geometric parameters are reproduced reasonably well by the quantum chemical calculations, except for the S-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).-O bond and -(C-S-O-C) ) 75(3)°. In the minor conformer (18(7)%), this CdO is oriented anti. Both conformers possess syn orientation of the CdO bond of the CF3C(O) group. The conformational properties and geometric parameters are reproduced reasonably well by the quantum chemical calculations, except for the S-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).dO is oriented anti. Both conformers possess syn orientation of the CdO bond of the CF3C(O) group. The conformational properties and geometric parameters are reproduced reasonably well by the quantum chemical calculations, except for the S-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).3C(O) group. The conformational properties and geometric parameters are reproduced reasonably well by the quantum chemical calculations, except for the S-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).-O bond length, which is predicted too long by 0.04 Å (B3LYP/aug-cc-pVTZ).