A solvent-free copper/iron-catalyzed N-arylation of nitrogen-containing heterocycles with trimethoxysilanes method for the formation of C–N bonds has been developed. In the presence of Cu, FeCl3, TBAF, and air, a variety of nitrogen-containing heterocycles including imidazoles and triazoles were coupled with aryltrimethoxysilanes and vinyltrimethoxysilane to afford the corresponding products in moderate to excellent yields. ...