The present report describes the preparation and characterization of several N-2- (trimethylsilyl) ethyl-N-nitrosocarbamates, designed as precursors to thermally unstable secondary N-nitrosocarbamate anions via fluoride-assisted cleavage. X-ray structural studies demonstrate that the core N-nitrosocarbamate moiety has a nearly planar geometry, with an sE orientation at the N–N bond. DFT calculations (B3LYP/6-31+ G (d)) reproduce ...