Transactions of the Faraday Society
Transactions of the Faraday Society was published from 1905 - 1971.
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Paper
Trans. Faraday Soc. , 1971, 67, 56 - 66, DOI: 10.1039/TF9716700056
Electron spin resonance studies of photo-oxidation by metal ions in rigid media at low temperatures. Part 1.—Ce(IV) photo-oxidation of alcohols
D. Greatorex and T. J. Kemp
Photolysis of deoxygenated solutions of ceric perchlorate and ceric ammonium nitrate in alcoholic, aqueous alcoholic and water + alcohol + acetonitrile solutions at 77 K by light of wavelength >300 nm leads to formation of radicals derived from the alcohol identified by electron spin resonance (e.s.r.) spectroscopy. Primary alcohols RCH2OH yield R
HOH but secondary alcohols R2CHOH yield R· in addition to, and sometimes to the exclusion of R2OH. Tertiary alcohols always give an alkyl fragment, e.g. C2H5· from tert-amyl alcohol. Allylic alcohols produce the corresponding hydroxyallyl radical and 1,2-diphenylethanol gives a spectrum of benzyl radical, indicating C—C cleavage. The mode of photo-oxidation by Ce(IV) clearly parallels that of the corresponding thermal oxidation.
