Mechanistic Insights on the Functionalization of CO2 with Amines and Hydrosilanes Catalyzed by a Zwitterionic Iridium Carboxylate‐Functionalized Bis‐NHC Catalyst

The zwitterionic complex [Cp*IrCl{(MeIm)2CHCOO}] (1) efficiently catalyzes the selective hydrosilylation of CO2 to afford the corresponding silylformate. The best reaction performance has been achieved in acetonitrile at 348 K using HSiMe2Ph. The 1‐catalyzed reaction of pyrrolidine with CO2 and HSiMe2Ph strongly depends on the CO2 pressure. At low concentration of CO2 (1 bar) formation of the corresponding silylcarbamate, by insertion of CO2 into the Si−N bond of the in situ generated silylamine was observed, while at higher pressure (3 bar) the formamide derivative was obtained as major reaction product. The unexpected formation of pyrrolidin‐1‐ium formate as intermediate of the reaction the 1‐catalyzed of CO2 with pyrrolidine and HSiMe2Ph has been observed, and its role in the formation of 1‐formylpyrrolidine rationalized. Moreover, a mechanism for the reaction of CO2 with hydrosilanes, in the presence and in the absence of amines, based on theoretical calculations has been proposed. Understanding CO2 reduction: The zwitterionic iridium complex catalyzes the reduction of CO2 with hydrosilanes to selectively afford the corresponding silylformates with the carboxylate fragment playing a key role. The mechanism of the reductive functionalization of CO2 with amines and hydrosilanes has been investigated both experimentally and by theoretical calculations