Hydrogen bond donors (HBD) are a sustainable privileged class of catalysts which are broadly used for the activation of compounds in synthetic chemistry. Among them, the metal-templated HBD complexes present...

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The metal-templated hydrogen bond donors (HBD) are prospective catalytic systems for the activation of organic molecules in chemical reactions. Here we report the application of the chiral cationic Co(III) complexes based on commercially available (S,S)-1,2-diaminocyclohexane and (R,R)-1,2-diphenylethylendiamine and salicylaldehydes with an iodide counter-anion as bifunctional one-component hydrogen bond donor/nucleophilic catalysts for the conversion of carbon dioxide with epoxides into valuable cyclic carbonates under solvent-and co-catalyst free conditions. We demonstrated that (R,R)-1,2-diphenylethylendiamine based complex Λ(R,R)-2 is superior to (S,S)-1,2-diaminocyclohexane based Δ(S,S)-1 a catalyzing the reaction at ambient conditions (RT and 1 bar CO 2 ). The TON and TOF values of 850 and 35 h À 1 , respectively, were achieved at low catalyst loading (0.1 mol %) at 10 bars of CO 2 and 100 °C. Furthermore, the Co(III) complexes catalyzed the reaction with diluted air/CO 2 mixture (15 vol % of CO 2 ) producing the desired styrene carbonate in up to 75% yield. A plausible catalytic cycle consistent with all experimental observations was proposed based on DFT calculations. The DFT calculations elucidated the difference in the ring opening step in cases of propylene oxide and styrene oxide. In addition, the kinetic resolution of terminal epoxides was observed with selectivity factor (s) of up to 1.6 in case of the complex Λ(R,R)-2.