Invited
Making molecules out of thin air

Benzene derivatives and dinitrogen are abundant resources, but it is difficult to activate the C-H and N-N bonds of these stable compounds. Here, we describe a system that breaks C-H bonds of simple arenes and inserts a nitrogen atom from N₂, resulting in the formation of aniline derivatives from arenes and N₂. A key to the process is the partial silylation of the N₂, which generates electrophilic intermediates that can engage the hydrocarbyl moiety. We elucidate the structures of several intermediates, and illuminate aspects of the mechanism such as the key C-H activation and the migration of an aryl ligand to the silylated N₂ fragment. These results point the way toward the use of N₂ as a synthon for N-containing organic molecules.