Cobalt(III) Complexes as Bifunctional Hydrogen-Bond Donor Catalysts Featuring Halide Anions for Cyclic Carbonate Synthesis at Ambient Temperature and Pressure: A Mechanistic Insight

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 CO2). The TON and TOF values of 850 and 35 h−1, respectively, were achieved at low catalyst loading (0.1 mol %) at 10 bars of CO2 and 100 °C. Furthermore, the Co(III) complexes catalyzed the reaction with diluted air/CO2 mixture (15 vol % of CO2) 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. © 2022 Wiley-VCH GmbH.

Emelyanov M.A.1 , Lisov A.A. 2, 3 , Medvedev M.G.3 , Maleev V.I. 1 , Larionov V.A. 1, 4
John Wiley and Sons Inc
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  • 1 A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilov Str. 28, Moscow, 119991, Russian Federation
  • 2 Department of Chemistry, Lomonosov Moscow State University, Leninskie, Gory 1/3, Moscow, 119991, Russian Federation
  • 3 N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky prospect 47, Moscow, 119991, Russian Federation
  • 4 Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklaya Str. 6, Moscow, 117198, Russian Federation
Ключевые слова
carbon dioxide fixation; cobalt complex; cyclic carbonate; DFT calculations; hydrogen bond donor
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