KETONE COUPLING ON REDUCED TIO2 (001) SURFACES - EVIDENCE OF PINACOL FORMATION
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Reductive coupling of acetone and acetophenone was investigated in temperature-programmed desorption (TPD) studies on both reduced (Ar+-bombarded) and oxidized TiO2 (001) surfaces. The principal reaction product of either ketone on the reduced surface was a symmetric olefin with twice the carbon number of the reactant. 2, 3-Diphenyl-2-butene comprised over 65%of the volatile carbon-containing species desorbed from the reduced surface following acetophenone adsorption. The main side reactions which yielded products of the same carbon number as the reactants included deoxygenation to form olefins and deoxygenation plus hydrogenation to yield saturated species. The yield of reduction products was greatly diminished on the oxidized TiO2 (001) surface; the yield of 2, 3-dimethyl-2-butene, the reductive coupling product of acetone, decreased 10-fold with respect to the yield from the reduced surface. This decrease in activity for reductive coupling is similar in scale to that observed for benzaldehyde coupling on the same surfaces, supporting the conclusion that both ketone and aldehyde coupling reactions occur at ensembles of Ti cations able to undergo a four-electron oxidation. Phenyl groups adjacent to the carbonyl carbon have the greatest effect on the carbonyl coupling reaction, giving significantly higher yields of the coupled olefin product. The observation of a small amount of the pinacol, 2, 3-diphenyl-2, 3-butanediol, during acetophenone TPD is the first direct evidence that the carbonyl coupling reaction on reduced TiO2 surfaces proceeds through a pinacolate intermediate, as it does for the McMurry reaction carried out in liquid-solid slurries. 1995, American Chemical Society. All rights reserved.