Role of pre-organization around the azaphosphatrane catalyst's active site in the conversion of CO2 to cyclic carbonates

•Azaphosphatranes in the synthesis of styrene carbonate from CO2 and epoxides•Substitution tuning at the PH+ site led to increased activity and robustness.•H-bonding between F or OMe groups and PH+ results in larger stabilizing effects.

Various N-substituted azaphosphatranes have been prepared and successfully applied to the synthesis of styrene carbonates from CO2 and epoxides. Enhancement of the catalytic properties of the azaphosphatrane was achieved upon pre-organization of the active site through hydrogen-bonding.

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