Hydrogenation of CO2‐Derived Carbonates and Polycarbonates to Methanol and Diols by Metal–Ligand Cooperative Manganese Catalysis

The first base‐metal‐catalysed hydrogenation of CO2‐derived carbonates to alcohols is presented. The reaction proceeds under mild conditions in the presence of a well‐defined manganese complex with a loading as low as 0.25 mol %. The non‐precious‐metal homogenous catalytic system provides an indirect route for the conversion of CO2 into methanol with the co‐production of value‐added (vicinal) diols in yields of up to 99 %. Experimental and computational studies indicate a metal–ligand cooperative catalysis mechanism.