Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN

The dipolar oxathiazyne‐like sulfinylnitrene RS(O)N, a highly reactive α‐oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF 3 S(O)N 3 at 350 °C, an elusive sulfinylnitrene CF 3 S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix‐isolation IR spectroscopy. Further fragmentation of CF 3 S(O)N at 600 °C produced CF 3 and a novel iminyl radical OSN, an SO 2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF 3 S(O)N 3 .