Deciphering the Mechanism of Base-Triggered Conversion of Ammonia to Molecular Nitrogen and Methylamine to Cyanide

We report an in-depth investigation into the ammonia oxidation mechanism by the catalyst [Ru^III(tpy)(dmabpy)NH₃]³⁺ ([Ru(NH₃)]³⁺). Stoichiometric reactions of [Ru(NH₃)]³⁺ were carried out with exogenous noncoordinating bases to trigger a proposed redox disproportionation reaction, which was followed using variable-temperature NMR spectroscopy. An intermediate species was identified as a dinitrogen-bridged complex using ¹⁵N NMR and Raman spectroscopy on isotopically labeled complexes. This intermediate is proposed to derive from coupling of nitridyl species formed upon sequential redox disproportion reactions. Acetonitrile displaces the dinitrogen bridge to yield free N₂. DFT calculations support this lower-energy pathway versus that previously reported for ammonia oxidation by the parent [Ru^III(tpy)(bpy)NH₃]³⁺ complex. These experimental and computational results are consistent with the interpretation of redox disproportionation involving sequential hydrogen atom transfer reactions by an amide/aminyl intermediate, [Ru(NH₂)^-]⁺ ⇔ [Ru(NH₂)^•]⁺, formed upon deprotonation of the parent complex. Control experiments employing a large excess of ammonia as a base indicate this new proposed lower-energy pathway contributes to the oxidation of ammonia to dinitrogen in conditions relevant to electrocatalysis. In addition, analogous methylamine complexes, [Ru(NH₂CH₃)]^2+/3+, were prepared to further test the proposed mechanism. Treating [Ru(NH₂CH₃)]³⁺ with a base cleanly yields two products [Ru(NH₂CH₃)]²⁺ and [Ru(CN)]⁺ in an ∼3:1 ratio, fully consistent with the proposed cascade of hydrogen atom transfer reactions by an intermediate.