Considering Electrocatalytic Ammonia Synthesis via Bimetallic Dinitrogen Cleavage

Despite advances in the development of molecular catalysts capable of reducing dinitrogen to ammonia using proton donors and chemical reductants, few molecular electrocatalysts have been discovered. This Perspective considers the prospects of electrocatalyst development based on a mechanism featuring the cleavage of N-2 into metal nitride complexes. By understanding the factors that control the reactivity of individual steps along the electrochemical N-2 cleavage path, opportunities for new advances are identified. Ligand design principles for facile electrochemical N-2 binding, formation of bridging N-2 complexes, thermal or photochemical N-2 cleavage, and conversion of a nitride ligand into ammonia are described, featuring recent advances and the authors’ collaborative work on rhenium complexes.