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.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:594960 |
| Date | January 1971 |
| Creators | Greatorex, David |
| Publisher | University of Warwick |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://wrap.warwick.ac.uk/67007/ |
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