Photolysis of 1,1,1‐trifluoromethylazomethane as a source of methyl and trifluoromethyl radicals

The photochemistry of 1,1,1‐trifluoromethylazomethane has been partially characterized. The quantum yield for N 2 formation from photolysis at 366 nm and room temperature was unity at low pressure and decreased to 0.5 at 630 torr. At room temperature the principal products were C 2 H 6 , C 2 F 6 , CH 3 CF 3 (or CH 2 CF 2 + HF at reduced pressures), plus substituted hydrazines, which mainly arise from addition of CF 3 to the parent followed by combination of these radicals with CH 3 or CF 3. These fluorinated methyl hydrazine products detract from the general utility of CF 3 ‐N 2 ‐R compounds as sources for simultaneous study of the chemistry of CF 3 and R radicals. At room temperature the hydrazine products accounted for more than 50% of the total yield; however, these products can be reduced by lowering the temperature and at 195°K their yields are negligible. The quantum yield for intramolecular (direct) formation of CH 3 CF 3 + N 2 was shown to be ≤0.002.