Contrasting Photolytic and Thermal Decomposition of Phenyl Azidoformate: The Curtius Rearrangement Versus Intramolecular C–H Amination

The decomposition of phenyl azidoformate, PhOC­(O)­N₃, was studied by combining matrix isolation spectroscopy and quantum chemical calculations. Upon UV laser photolysis (193 and 266 nm), the azide isolated in cryogenic noble gas matrices (Ne and Ar, 2.8 K) decomposes into N₂ and a novel oxycarbonylnitrene PhOC­(O)­N, which was identified by matrix-isolation IR spectroscopy (with ¹⁵N labeling) and EPR spectroscopy (|<i>D</i>/<i>hc</i>| = 1.620 cm^–1 and |<i>E</i>/<i>hc</i>| = 0.024 cm^–1). Subsequent visible-light irradiation (532 nm) causes rearrangement of the nitrene into phenoxy isocyanate PhONCO with complex secondary fragmentation (PhO· + ·NCO) and radical recombination species in matrices. The observation of PhONCO provides solid evidence for the Curtius rearrangement of phenyl azidoformate. In sharp contrast, flash vacuum pyrolysis (FVP) of PhOC­(O)­N₃ at 550 K yields N₂ and exclusively the intramolecular C–H amination product 3<i>H</i>-benzooxazol-2-one. FVP at higher temperature (700 K) leads to further dissociation into CO₂, HNCO, and ring-contraction products. To account for the very different photolytic and thermal decomposition products, the underlying mechanisms for the Curtius rearrangement (concerted and stepwise) of PhOC­(O)­N₃ and the intramolecular C–H amination of the nitrene in both singlet and triplet states are discussed with the aid of quantum chemical calculations using the B3LYP, CBS-QB3, and CASPT2 methods