Abstract
Two carbonyl pseudohalogen compounds CF2HC(O)NCO and CF2HC(O)NCS have been synthesized and fully characterized by IR (gas-phase, matrix-isolation), Raman (liquid), UV–vis (gas-phase), and NMR (19F, 13C, 1H) spectroscopy. The conformational properties and photochemistry of both species have been studied by combining matrix-isolation IR spectroscopy and quantum chemical calculations with the B3LYP, MPW1PW91, CBS-QB3 methods. Two conformers (syn and anti), depending on the configuration between the CO and pseudohalogen ligands (NCO and NCS), have been unambiguously identified in both gas phase and solid noble gas matrices (Ar and Ne). Consistent with the theoretical calculations, the syn conformation is energetically more favorable. Upon irradiation with an ArF excimer laser (193 nm), CF2HC(O)NCO and CF2HC(O)NCS in cryogenic matrices eliminate CO and yield CF2HNCO and CF2HNCS, respectively. The underlying mechanism for the photochemistry of CF2HC(O)NCO is rationalized by the elimination of the carbonyl rather than the isocyanato CO moiety.
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