Greatorex, David (1971) Electron spin resonance studies of photo-oxidation by metal ions. PhD thesis, University of Warwick.

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Abstract

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.

Item Type:	Thesis (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Electron paramagnetic resonance, Oxidation, Metal ions
Official Date:	September 1971
Dates:	Date Event September 1971 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Kemp, T. J. (Terence James)
Sponsors:	Science Research Council (Great Britain)
Extent:	104 leaves
Language:	eng

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