An EPR study of a radical anion in x-ray irradiated trifluoroacetamide single crystals at 3 K

Abstract
The radical anion CF3ĊONH2− was identified by EPR spectroscopy in a single crystal of trifluoroacetamide x-ray irradiated at 3 K. The primary radical gave anisotropic hyperfine couplings to a fluorine of 139, 78, and 63 G, with g values 2.0061, 2.0047, and 2.0029. The maximum fluorine coupling is directed close to one of the C–F bonds, indicating a delocalization of spin density into that bond. The radical anion decomposes thermally by defluorination, giving ĊF2CONH2. By bleaching the anion with visible light a ĊF3 fragment is formed. A complete reaction mechanism both for the primary oxidation and reduction products consistent with the observed species is proposed.

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