Oxime Ether Radical Cations Stabilized by N‐Heterocyclic Carbenes

N‐heterocyclic carbene (NHC) nitric oxide (NHCNO) radicals, which can be regarded as iminoxyl radicals stabilized by NHCs, were found to react with a series of silyl and alkyl triflates to generate the corresponding oxime ether radical cations. The structures of the resulting oxime ether radical cations were determined by X‐ray crystallography, along with EPR and computational analysis. In contrast, lutidinium triflate produced a 1:1 mixture of NHCNO⁺]OTf^?] and NHCNHOH⁺]OTf^?] upon the reaction with NHCNO. This study adds an important example of stable singlet carbenes for stabilizing main‐group radicals because of their π‐conjugating effect, the synthesis and structures of which have not been reported previously.