Di-Silyl Rhodium(III) and Iridium(III) Complexes as Catalysts in Carbene Insertion Reactions into Hydrosilanes

Catalytic carbene insertion into Si–H bonds has been recognized as an important strategy for the formation of new Si–C bonds. Herein, we report the synthesis and characterization of two new iridium(III) complexes bearing silyl–quinoline ligands (SiN, 8-(dimethylsilyl)quinoline): a neutral dimeric species [IrCl(SiN)2]2 (3) and a cationic monomeric complex {Ir(SiN)2(NCMe)2}[BArF4] (4). These iridium complexes, together with their rhodium analogues previously reported by our group [RhCl(SiN)2] (1) and [Rh(SiN)2(NCMe)][BArF4] (2), were evaluated as catalysts for the insertion reaction of diazoacetates into various hydrosilanes. These studies demonstrate the catalytic activity of di-silyl rhodium(III) and iridium(III) complexes in carbene insertion into Si–H bonds, providing the first example of a rhodium(III) complex catalyzing this reaction.