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

The dipolar oxathiazyne-like sulfinylnitrene RS(O) N, a highly reactive alpha-oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF3S(O) N-3 at 350 degrees C, an elusive sulfinylnitrene CF3S(O) N was generated in the gas phase in its singlet ground state and was characterized by matrix-isolation IR spectroscopy. Further fragmentation of CF3S(O) N at 600 degrees C produced CF3 and a novel iminyl radical OSN, an SO2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF3S(O) N-3.