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 N2 into metal nitride complexes. By understanding the factors that control the reactivity of individual steps along the electrochemical N2 cleavage path, opportunities for new advances are identified. Ligand design principles for facile electrochemical N2 binding, formation of bridging N2 complexes, thermal or photochemical N2 cleavage, and conversion of a nitride ligand into ammonia are described, featuring recent advances and the authors’ collaborative work on rhenium complexes.

A previously reported cobalt complex featuring a tetraimidazolyl-substituted pyridine chelate is an active water oxidation electrocatalyst with moderate overpotential at pH 7. While this complex decomposes rapidly to a less-active species under electrocatalytic conditions, detailed electrochemical studies support the agency of an initial molecular catalyst. Cyclic voltammetry measurements confirm that the imidazolyl donors result in a more electron-rich Co center when compared with previous pyridine-based systems. The primary changes in electrocatalytic behavior of the present case are enhanced activity at lower pH and a marked dependence of catalytic activity on pH.

Oxidative addition is an essential elementary reaction in organometallic chemistry and catalysis. While a diverse array of oxidative addition reactions has been reported to date, examples of P−O bond activation are surprisingly rare. Herein, we report the ligand-templated oxidative addition of a phosphinite P−O bond in the diphosphinito aniline compound HN(2-OP i Pr 2 -3,5-t Bu-C 6 H 2 ) 2 [H(P 2 ONO)] at Ni 0 to form (PONO)Ni(HP i Pr 2 ) after proton rearrangement. Notably, the P−O cleavage occurs selectively over an amine N−H bond activation. Additionally, the ligand cannibalization is reversible, as addition of XPR 2 (X = Cl, Br; R = i Pr, Cy) to (PONO)Ni(HP i Pr 2 ) readily produces either symmetric or unsymmetric (P 2 ONO)NiX species and free HP i Pr 2 . Finally, the mechanisms of both the initial P−O bond cleavage and its subsequent reconstruction are investigated to provide further insight into how to target P−O bond activation.

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