THE PYROLYSIS OF TETRANITROMETHANE IN THE GAS-PHASE

C(NO2)4, one of the methane derivatives with the largest oxygen content (>65 wt.%) and therefore not exactly hazard-free, decomposes in the gas phase at 10(-5) mbar and 610 K exclusively into the gaseous products .NO2, .NO, CO2, and CO. Together with the known kinetics for a radical dissociation as the first step, the temperature-dependent photoelectronic spectra and comprehensive quantum chemical calculations enable a mechanism to be proposed that explains all experimental findings. Conversions on silver wool and charcoal, and the cothermolysis of dimethylamine and dimethylnitramine suggest possibilities for further investigations.