Evidences in favour of a single electron transfer (SET) mechanism in the TiO2 sensitized photo-oxidation of α-hydroxy- and α,β-dihydroxybenzyl derivatives in water

The TiO2 photosensitized oxidation in water of a series of X-ring substituted benzyl alcohols gives the corresponding benzaldehyde. Kinetic evidence (from competitive experiments) suggests a single electron transfer (SET) mechanism with a changeover of the electron abstraction site from the aromatic moiety (X = 4-OCH3, 4-CH3, H and 3-Cl) to the hydroxylic group (X = 3-CF3 and 4-CF3), probably due to the preferential adsorption of the above OH group on the TiO2 surface. The same photo-oxidation of a series of 1-(X-phenyl)-1,2-ethanediols and of 2-(X-phenyl)-1,2-propanediols gives the corresponding benzaldehyde and acetophenone, respectively, accompanied by formaldehyde, whereas a series of symmetrically X-ring-substituted 1,2-diphenyl-1,2-ethanediols yields the corresponding benzaldehyde (substrate/product molar ratio = 0.5). The relative rate values suggest a SET mechanism in all of the series, with electron abstraction from one of the two OH groups of all the considered diols, probably due to the much higher adsorption of the above groups (due to the chelation effect) on the semiconductor. Further confirmation of this mechanistic behaviour has been obtained from laser flash photolysis experiments.