Prospects for Forming C–N Bonds from Dinitrogen

The formation of C–N bonds from molecular dinitrogen (N2) offers a synthetic route to value-added nitrogen-containing compounds without relying on prefunctionalized nitrogen sources. This Perspective highlights recent advances in forming C–N bonds from N2 with homogeneous transition metal complexes. After discussing how transition metal complexes activate N2 through various coordination modes, we focus on the reactivity of reduced nitrogen intermediates with different kinds of carbon sources. Carbon electrophiles and nucleophiles enable C–N bond formation via insertion, substitution, or radical pathways. Cycloaddition reactions, particularly involving polarized N2 ligands and unsaturated carbon electrophiles, offer routes to more complex products. We describe efforts to achieve catalytic turnover and emphasize the remaining obstacles to catalytic C–N bond construction.