Abstract

AbstractThe simplest aminosulfinyl radical H2NSO has been generated in the gas phase through flash vacuum pyrolysis of CF3S(O)NH2 at approximately 1000 K. Upon UV light irradiation (365 nm), 1,3‐H migration occurs in H2NSO and furnishes an elusive N‐amidyl radical HNSOH in syn and anti conformations in cryogenic matrices (N2 or Ar, 15 K). Further 266 nm laser irradiation results in dissociation of HNSOH to H2O and SN and concomitant reformation of H2NSO in trace amount. The identification of H2NSO, syn‐HNSOH, and anti‐HNSOH by matrix‐isolation IR spectroscopy is supported by high‐level quantum chemical computations.

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