Photolysis of O2-CT Complexes

The phenomenon of the concurrent action of light and air on organic compounds, leading under certain conditions to the formation of substances that are more powerful oxidants than oxygen itself, has interested chemists for a long time. Peroxidic compounds were obtained from alcohols (48-56) and ethers (57-64) through the action of ultraviolet and/or visible light in the presence of O2. It is certain that for the most part these reactions did not reflect the photochemistry of O2-CT complexes but were sensitized by carbonyl compounds and other impurities. This must be especially true for aqueous and neat alcohols since it was practically impossible at the time to ensure the absence of such impurities. 

A rearrangement of this dative peroxide could then lead to ordinary peroxide. A thought along similar lines had already been expressed in 1897 by Bach (68).  

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In recent years a certain amount of experimental material on the photolysis of O2-CT complexes from ethers and amines has become available whereas no such work seems to have been done during this time on alcohols. This discussion is therefore restricted to the former two classes of compounds. 

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