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Title: Electron spin resonance studies of photo-oxidation by metal ions
Author: Greatorex, David
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 1971
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The e.s.r. technique has been applied to the study of primary processes occurring during photo-induced electron transfer reactions between metal ions and organic substrates. Photolysis of deoxygenated solutions of ceric perchlorate and ceric ammonium nitrate in alcoholic, aqueous alcoholic and water/alcohol/aceto-nitrile solutions at 770K by light of wavelength > 300 nm leads to formation of radicals derived from the alcohol. Primary alcohols, R CH2OH, yield R CHOH but secondary alcohols, R2CHOH, yield R' in addition to, and sometimes to the exclusion of, R2COH. Tertiary alcohols always give an alkyl fragment, e.g. C2H5', from 1,1-dimethylpropan-1-ol. 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 CeIV clearly parallels that of the corresponding thermal reaction.
Supervisor: Not available Sponsor: Science Research Council (Great Britain)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry