An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO2with epoxides under ambient conditions

Hydrogen bond donors (HBDs) 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 perspective systems with high catalytic potential. In this respect, here we report the design of the next-generation octahedral Co(iii) complexes based on cheap commercially available 1,2-phenylenediamine and 3,5-di-tert-butyl-salicylaldehyde. It was shown that the obtained Co(iii) complex with an iodide counter-anion operates as a bifunctional one-component hydrogen bond donor/nucleophilic catalyst for the fixation of carbon dioxide with epoxides into valuable cyclic carbonates under ambient conditions (RT and 1 bar CO2) and solvent- and co-catalyst-free conditions. The TON and TOF values of 38 and 1.6, respectively, were achieved at a low catalyst loading (2 mol%) under ambient conditions. Furthermore, the obtained Co(iii) complex catalyzed the reaction with a diluted air/CO2 mixture (15 vol% of CO2) producing the desired cyclic carbonate in a 92% yield. A plausible catalytic cycle consistent with all experimental observations was proposed based on DFT calculations. The epoxide-opening step was found to be the rate-determining step. Besides, the influence of different additives on the catalysis was investigated and explained computationally. This journal is © the Partner Organisations.

Emelyanov M.A.1 , Stoletova N.V.1 , Lisov A.A.2, 3 , Medvedev M.G.3 , Smol'Yakov A.F. 1 , Maleev V.I. 1 , Larionov V.A. 1, 4
Royal Society of Chemistry
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  • 1 A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), 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
Additives; Carbon dioxide; Catalysis; Catalysts; Complexation; Design for testability; Drug products; Hydrogen bonds; Ambient conditions; Catalyst loadings; Catalytic potential; Fixation of carbon dioxide; Hydrogen bond donors; Perspective systems; Rate determining step; Synthetic chemistry; Cobalt compounds
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