Ammonia (electro)­oxidation with molecular catalysts is a rapidly developing topic with wide practical applications ahead. We report here the catalytic ammonia oxidation reaction (AOR) activity using [Ru­(tda-κ-N3O)­(py)2], 2, (tda2– is 2,2′:6′,2′′-terpyridine-6,6′′-dicarboxylate; py is pyridine) as a catalyst precursor. Furthermore, we also describe the rich chemistry associated with the reaction of Ru-tda and Ru-tPa (tPa–4 is 2,2′:6′,2′′-terpyridine-6,6′′-diphosphonate) complexes with NH3 and N2H4 using [RuII(tda-κ-N3O)­(dmso)­Cl] (dmso is dimethyl sulfoxide) and [RuII(tPa-κ-N3O)­(py)2], 8, as synthetic intermediates, respectively. All the new complexes obtained here were characterized spectroscopically by means of UV–vis and NMR. In addition, a crystal X-ray diffraction analysis was performed for complexes trans-[RuII(tda-κ-N3)­(py)2(NH3)], 4, trans-[RuII(tda-κ-N3)­(N-NH2)­(py)2], 5, cis-[RuII(tda-κ-N3)­(py)­(NH3)2], 6 (30%), and cis-[RuII(tda-k-N3)­(dmso)­(NH3)2], 7 (70%). The AOR activity associated with 2 and 8 as catalyst precursors was studied in organic and aqueous media. For 2, turnover numbers of 7.5 were achieved under bulk electrolysis conditions at an E app = 1.4 V versus normal hydrogen electrode in acetonitrile. A catalytic cycle is proposed based on electrochemical and kinetic evidence.

Molecular catalysts can promote ammonia oxidation, providing mechanistic insights into the electrochemical N 2 cycle for a carbon-free fuel economy. We report the ammonia oxidation activity of carbon anodes functionalized with the oligomer {[Ru II (bda-κ-N 2 O 2 )(4,4′bpy)] 10 (4,4′-bpy)}, Rubda-10, where bda is [2,2′-bipyridine]-6,6′dicarboxylate and 4,4′-bpy is 4,4′-bipyridine. Electrocatalytic studies in propylene carbonate demonstrate that the Ru-based hybrid anode used in a 3-electrode configuration transforms NH 3 to N 2 and H 2 in a 1:3 ratio with near-unity faradaic efficiency at an applied potential of 0.1 V vs Fc +/0 , reaching turnover numbers of 7500. X-ray absorption spectroscopic analysis after bulk electrolysis confirms the molecular integrity of the catalyst. Based on computational studies together with electrochemical evidence, ammonia nucleophilic attack is proposed as the primary pathway that leads to critical N−N bond formation.