The decomposition of benzenesulfonyl azide: a matrix isolation and computational study.

The thermal-decomposition and photo-decomposition of benzenesulfonyl azide, PhS(O)N, have been studied by combining matrix-isolation IR spectroscopy and quantum chemical calculations. Upon flash vacuum pyrolysis at 800 K, the azide splits off molecular nitrogen and exclusively furnishes phenylnitrene (PhN) and SO in the gas phase. In contrast, the azide favors stepwise photodecomposition in solid Ar and Ne matrices at 2.8 K. Specifically, the UV laser photolysis (193 and 266 nm) of PhS(O)N results in the formation of the key nitrene intermediate PhS(O)N in the triplet ground state, which undergoes pseudo-Curtius rearrangement into N-sulfonyl imine PhNSO under subsequent visible light irradiation (380-450 nm). Further fragmentation of PhNSO into SO and PhN followed by ring-expansion to didehydroazepine also occurs upon visible light irradiation. The preference of the stepwise mechanism for the decomposition of PhS(O)N is supported by quantum chemical calculations using DFT B3LYP/6-311++G(3df,3pd) and CBS-QB3 methods.