Electron spin resonance studies of photo-oxidation by metal ions in rigid media at low temperatures. Part 4.—Survey of photo-oxidation by the uranyl ion
- 1 January 1972
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 68, 2059-2076
- https://doi.org/10.1039/f19726802059
Abstract
The long-standing problem of the mechanism of photo-oxidation of organic and inorganic molecules by the UO2+ 2 ion has been explored in some detail by the matrix isolation method, the detection of trapped substrate-derived radicals being effected by electron spin resonance spectroscopy, mostly using organic matrices at 77 K. A variety of mechanisms is apparent even within a given homologous series, but the most common feature is abstraction of a hydrogen atom from a carbon atom adjacent to an activating group such as —CO—, —CN, —CO2H, —CHO, —OH, —CONH2, —CO2R or from a phosphorus atom; carbon-carbon cleavage is found (sometimes exclusively) with secondary and tertiary alcohols, ketones, some carboxylic acids and diethyl ether. These results are discussed in the light of recent steady-state studies involving comparison of quantum yield and fluorescence quenching data.Keywords
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