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 at Ambient ConditionsстатьяНаучно-популярная статья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 8 сентября 2021 г.
Аннотация: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 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 at ambient conditions (RT and 1 bar CO2) under solvent and co-catalyst free conditions. The TON and TOF values of 38 and 1.6, respectively, were achieved at low catalyst loading (2 mol%) under ambient conditions. Furthermore, the obtained Co(III) complex catalyzed the reaction with 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. Besides, the influence of different additives on the catalysis was investigated and explained computationally.