Abstract:
A survey is presented of the primary processes in the photo-oxidation by Ce(IV) ions at 77 K of a variety of organic molecules classified by functional group; these processes have been determined by characterization of the resulting organic free radical by electron spin resonance spectroscopy. Aldehydes RCHO and aldehyde hydrates RCH(OH)2 are oxidized to RĊO and RĊC(OH)2 respectively, although C2H5ĊO disappears at 120 K, producing instead CH3ĊHCHO. Ketones produce either the alkyl radical R from RCOR′ or the radical derived by abstraction of a hydrogen atom from the methylene or methine groups adjacent to the carbonyl group; in some cases both types of radical are discernible. Esters also undergo C—H or C—C fission processes depending on the degree of substitution of the R fragment of RCO2R′, whilst formamide yields a spectrum of ·CONH2. Methyl methacrylate yields a vinylic monomer radical at 77 K which induces polymerization at 175 K to give the polymethyl methacrylate radical.
