Beyond Ammonia: Nitrogen-Element Bond Forming Reactions with Coordinated Dinitrogen.

The functionalization of coordinated dinitrogen to form nitrogen-element bonds en route to nitrogen-containing molecules is a long-standing challenge in chemical synthesis. The strong triple bond and the nonpolarity of the N molecule pose thermodynamic and kinetic challenges for promoting reactivity. While heterogeneous, homogeneous, and biological catalysts are all known for catalytic nitrogen fixation to ammonia, the catalytic synthesis of more complicated nitrogen-containing organic molecules has far less precedent. The example of silyl radical additions to coordinated nitrogen to form silylamines stands as the lone example of a catalytic reaction involving N to form a product other than ammonia. This Review surveys the field of molecular transition metal complexes as well as recent boron examples for the formation of nitrogen-element bonds. Emphasis is placed on the coordination and activation modes of N in the various metal compounds from across the transition series and how these structures can rationally inform reactivity studies. Over the past few decades, the field has evolved from the addition of carbon electrophiles in a manner similar to that of protonation reactions to more organometallic-inspired reactivity, including insertions, 1,2-additions, and cycloadditions. Various N-C, N-Si, and N-B bond-forming reactions have been discovered, highlighting that the challenge for catalytic chemistry is not in the reactivity of coordinated dinitrogen but rather removal of the functionalized ligand from the coordination sphere of the metal.