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The rich redox chemistry of nitrosoarenes has rendered these reactive molecules very useful in mod synthetic and material chemistry.Electrochemical studies have revealed the capability of nitrosoarenes to undergo one-electron oxidation or reduction reaction for a long time.However,the isolation and structural characterization of nitrosoarene radical compounds deviating the stabilization of transition-metal have not been achieved.Investigation on the reduction reaction of nitrosoarenes bearing steric demanding substituents has now revealed that the interaction of 2,6-dimesityl-1-nitroso-benzene (DmpNO) or 2,4,6-tri(tert-butyl)-1-nitroso-benzene (TtpNO) with KC8 and crypt-2,2,2 can produce the corresponding anion radical compound [K(crypt-2,2,2)][DmpNO] (1) or [K(crypt-2,2,2)][TtpNO] (2) in good isolated yield.Compounds 1 and 2 represent the first examples of isolable nitrosoarene radical compounds deviating the stabilization of transition-metal,and have been characterized by single-crystal X-ray diffraction study,electron paramagnetic resonance (EPR) spectroscopy,and elemental analysis.Theoretical study in collaboration with the characterization data revealed that the unpaired spin in [DmpNO]·-and [TtpNO]·-delocalizes on the nitroso and the central phenyl groups.