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Electron spin resonance studies of photo-oxidation by metal ions
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Greatorex, David (1971) Electron spin resonance studies of photo-oxidation by metal ions. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b1733314~S1
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) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Electron paramagnetic resonance, Oxidation, Metal ions | ||||
Official Date: | September 1971 | ||||
Dates: |
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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Publication Status: | Unpublished | ||||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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