Solvent‐Free Iridium‐Catalyzed Reactivity of CO 2 with Secondary Amines and Hydrosilanes

The complex [Ir(H)(CF 3 SO 3 )(NSiN)(coe)] (NSiN=bis(pyridine‐2‐yloxy)methylsilyl fac ‐coordinated) ( 1 ) is an effective catalyst precursor for the solvent‐free synthesis of silyl carbamates from reaction of aliphatic secondary amines with CO 2 and HSiMe(OSiMe 3 ) 2 . The preferential formation of the silyl carbamate instead of the expected formamide or methylamine has proven to be consequence of an iridium‐catalyzed dehydrogenative Si−N coupling between the silane and the amine to afford the corresponding silyl amine, which under the reaction conditions reacts with CO 2 to give the corresponding silyl carbamate.