Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity
as an intermediate for the production of a large number of industrial chemicals. Since
dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous
precious-metal-based catalysts and high temperatures are usually required for this reaction
to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at
room temperature catalysed by o-aminophenol (apH2), o-aminophenolate (apH) and the
non-precious metal complex trans-[FeII(apH)2(MeOH)2]. Under excitation at 289±10nm
and in the absence of additional photosensitizers, these photocatalysts generate hydrogen
and formaldehyde from anhydrous methanol with external quantum yields of 2.9±0.15%,
3.7±0.19% and 4.8±0.24%, respectively, which are the highest values reported so far to the
best of our knowledge. Mechanistic investigations reveal that the photo-induced formation of
hydrogen radicals triggers the reaction.
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