The Origin of the Activity of Amine‐Functionalized Metal–Organic Frameworks in the Catalytic Synthesis of Cyclic Carbonates from Epoxide and CO2

What a pair! MOF MIL-68(In)-NH2 was used to catalyze the synthesis of styrene carbonate from styrene oxide and CO2. Amine substitution on the linker of MIL-68(In) promotes the synthesis of cyclic carbonate from styrene epoxide and CO2. Ab initio calculations and in situ characterization indicate that ligand substitution has a larger impact through electronic effects on the Brønsted site than through CO2 activation.