Cobalt‐Catalyzed Transformation of Molecular Dinitrogen into Silylamine under Ambient Reaction Conditions

The first successful example of cobalt‐catalyzed reduction of N 2 with Me 3 SiCl and Na as a reductant, under ambient reaction conditions, gives N(SiMe 3 ) 3 , which can be readily converted into NH 3 . In this reaction system, 2,2′‐bipyridine (bpy) is found to work as an effective additive to improve substantially the catalytic activity. CoN 2 complexes bearing three Me 3 Si groups as ancillary ligands are considered to work as key reactive species based on DFT calculations. The DFT results also allow the proposal of a detailed reaction pathway for the transformation of N 2 into N(SiMe 3 ) 3 .