Abstract

The in situ photolysis of molecular fluorine and NO2 molecules in nitrogen matrices at 8°K yields the FN-bonded nitryl fluoride, FNO2, as the primary reaction product. However, controlled fluorine atom diffusion at 20°K, in the absence of photolytic radiation, results in the formation of the highly reactive, FO-bonded, nitrosyl hypofluorite, ONOF. Infrared absorptions at 1716.4, 1199.9, 702.3, and 411.9 cm−1 were assigned to this species, which was shown from 15N and 18O isotopic studies to contain two nonequivalent oxygen atoms. The ONOF molecule undergoes intramolecular photorearrangement at wavelengths below 400 nm to produce the more stable FNO2 form.

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