Conversion of Dinitrogen to Nitriles at a Multinuclear Titanium Framework

At present, ammonia (NH3), produced by the energy-intensive Haber-Bosch process, is the only nitrogen source for the industrial preparation of nitrogen-containing organic products. Although the activation and functionalization of dinitrogen (N-2) under milder conditions have received much recent interest, studies on the direct use of N-2 as a feedstock for organic synthesis are still in their infancy. Herein we report the synthesis of nitriles using titanium-activated nitrogen species as a nitrogen source. We have found that a mixed diimide/dinitride tetranuclear titanium complex generated by N-2 activation serves as a unique platform for the synthesis of nitriles through reaction with acid chlorides. This protocol features simple reaction condition (60 degrees C in benzene), no requirement for extra reagents, and unprecedented functional group tolerance (compatible with aromatic C-X (X = Cl, Br, I) bonds, nitro group, and ammonia-sensitive aldehyde and chloromethyl moieties).