The instances of coupling abiological reduction of carbon dioxide1,2 with other organic reaction are rare in the literature. Our group has reported Keplerate {Mo132} catalyzed reduction of CO2 to formic acid coupled with organic transformation from phenylacetylene to acetophenone under visible light irradiation.3 The protons generated by the CO2 reduction were taken up for oxidation of organic substrates. The whole reaction is thus driven by protons generated in the medium due to the water oxidation catalyzed by {Mo132-CO2} unit under visible light irradiation. The triple bonds act as Lewis basic site during hydration of phenylacetylene and are attacked by the protons in the medium and generate a vinylic carbocation. This addition of protons follows Markovnikov’s addition. The water then reacts with the carbocation and tautomerizes to give acetophenone. Thus, the reaction is driven by the photo-redox and acidic properties of Janus catalyst {Mo132}, which prove to be a key factor in driving the catalytic cycle.

Light-driven carbon dioxide reduction coupled with conversion of acetylenic group to ketone by a functional Janus catalyst based on keplerate {Mo132}

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27th CRSI National Symposium in Chemistry

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