Chloro- and dichloro-methylsulfonyl nitrenes, CH₂ClS(O)₂N and CHCl₂S(O)₂N, have been generated from UV laser photolysis (193 and 266 nm) of the corresponding sulfonyl azides CH₂ClS(O)₂N₃ and CHCl₂S(O)₂N₃, respectively. Both nitrenes have been characterized with matrix-isolation IR and EPR spectroscopy in solid N₂ (10 K) and glassy toluene (5 K) matrices. Triplet ground-state multiplicity of CH₂ClS(O)₂N (|D/hc| = 1.57 cm-1 and |E/hc| = 0.0026 cm-1) and CHCl₂S(O)₂N (|D/hc| = 1.56 cm-1 and |E/hc| = 0.0042 cm-1) has been confirmed. In addition, dichloromethylnitrene CHCl₂N (|D/hc| = 1.57 cm-1 and |E/hc| = 0 cm-1), formed from SO₂-elimination in CHCl₂S(O)₂N, has also been identified for the first time. Upon UV light irradiation (365 nm), the two sulfonyl nitrenes R⁻S(O)₂N (R = CH₂Cl and CHCl₂) undergo concomitant 1,2-R shift to N-sulfonlyamines R⁻NSO₂ and 1,2-oxygen shift to S-nitroso compounds R⁻S(O)NO, respectively. The identification of these new species with IR spectroscopy is supported by 15N labeling experiments and quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level. In contrast, the thermally-generated sulfonyl nitrenes CH₂ClS(O)₂N (600 K) and CHCl₂S(O)₂N (700 K) dissociate completely in the gas phase, and in both cases, HCN, SO₂, HCl, HNSO, and CO form. Additionally, ClCN, OCCl₂, HNSO₂, •NSO₂, and the atmospherically relevant radical •CHCl₂ are also identified among the fragmentation products of CHCl₂S(O)₂N. The underlying mechanisms for the rearrangement and decomposition of CH₂ClS(O)₂N and CHCl₂S(O)₂N are discussed based on the experimentally-observed products and the calculated potential energy profile.
Keywords: azides; decomposition; matrix isolation; nitrenes; photoisomerization; reaction mechanism.