Observation of Perfluoromethylnitrene in Cryogenic Matrixes

Abstract

Photolysis (254 nm) of CF 3 N 3 in pentane at 6−10 K produced a persistent electron paramagnetic resonance spectrum typical of a triplet nitrene centered at 8620 G. The spectrum (|D/hc| = 1.736 cm -1 ) is attributed to triplet CF 3 −N, and is very similar to that of triplet NH (|D/hc| = 1.863 cm -1 ) and CH 3 - N (|D/hc| = 1.720 cm -1 ) which were reported previously. CF 3 N 3 was also deposited in an argon matrix at 14 K. The azide (λ max = 257 nm) was decomposed by exposure to 254 nm light with the concurrent formation of sharp, structured absorption bands at 342, 347.5, and 354 nm. The UV bands are assigned to the triplet nitrene CF 3 N on the basis of its similarity to the spectrum of CH 3 N and time-dependent density functional theory (B3LYP) calculations.