The H2CCN and H2CNC radicals are observed in matrix IR spectra from acetonitrile exposed to radiation from laser ablation of transition metals, whereas cyc-H2CCN, another plausible isomer, is not. Density functional frequency calculations and D and C-13 isotopic substitutions substantiate the vibrational assignments. The cyano methyl radical converts to the 95 kJ/mol higher energy isocyano counterpart on uv photolysis. Computations show that the cyclic isomer is a shallow energy minimum between two transition states. Intrinsic reaction coordinate calculations indicate that conversion between the two products is feasible via the cyclic configuration.