An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO2 with epoxides under ambient conditions

An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO2 with epoxides under ambient conditions Full article

Journal

Inorganic Chemistry Frontiers
ISSN: 2052-1553 , E-ISSN: 2052-1545

Output data

Year: 2021, Volume: 8, Number: 16, Pages: 3871-3884 Pages count : 14 DOI: 10.1039/d1qi00464f

Authors

Emelyanov Mikhail A. ¹ , Stoletova Nadezhda V. ¹ , Lisov Alexey A. ^2,3 , Medvedev Michael G. ³ , Smol'yakov Alexander F. ¹ , Maleev Victor I. ¹ , Larionov Vladimir A. ^1,4

Affiliations

1	A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, Russian Federation
2	Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, 119991 Moscow, Russian Federation
3	N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky prospect 47, 119991 Moscow, Russian Federation
4	Peoples’ Friendship University of Russia (RUDN University)

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.

Emelyanov M.A. , Stoletova N.V. , Lisov A.A. , Medvedev M.G. , Smol'yakov A.F. , Maleev V.I. , Larionov V.A.
An octahedral cobalt(iii) complex based on cheap 1,2-phenylenediamine as a bifunctional metal-templated hydrogen bond donor catalyst for fixation of CO2 with epoxides under ambient conditions
Inorganic Chemistry Frontiers. 2021. V.8. N16. P.3871-3884. DOI: 10.1039/d1qi00464f WOS Scopus OpenAlex

≡ Web of science:	WOS:000673133500001
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