Relating N-H Bond Strengths to the Overpotential for Catalytic Nitrogen Fixation

Nitrogen (N₂) fixation to produce bio-available ammonia (NH₃) is essential to all life but is a challenging transformation to catalyse owing to the chemical inertness of N₂. Transition metals can, however, bind N₂ and activate it for functionalization. Significant opportunities remain in developing robust and efficient transition metal catalysts for the N₂ reduction reaction (N₂RR). One opportunity to target in catalyst design concerns the stabilization of transition metal diazenido species (M-NNH) that result from the first N₂ functionalization step. Well-characterized M-NNH species remain very rare, likely a consequence of their low N-H bond dissociation free energies (BDFEs). In this essay, we discuss the relationship between the BDFE_N-H of a given M-NNH species to the observed overpotential and selectivity for N₂RR catalysis with that catalyst system. We note that developing strategies to either increase the N-H BDFEs of M-NNH species, or to avoid M-NNH intermediates altogether, are potential routes to improved N₂RR efficiency.