OXIDATION OF DIFLUOROVINYLIDENE

Difluorovinylidene is a highly reactive and extremely electrophilic si nglet carbene that thermally abstracts an oxygen atom from CO2 at temp eratures as low as 30 K. The resulting difluoroketene is characterized for the first time using IR spectroscopy in combination with isotopic labeling and density functional theory (DFT) calculations. The three observed IR absorptions of the ketene at 1274, 1427, and 2162 cm(-1) a re assigned to the asymmetrical FCF stretching vibration and the asymm etrical and symmetrical CCO stretching vibrations, respectively. The o xidation of difluorovinylidene with O-3(2) results in a complex produc t mixture with CF2, C2F4, CO2, COF2, and CO as the major products. A m echanism consistent with all observed products is proposed.