Synthesis, Structure, and Ammonia Oxidation Catalytic Activity of Ru-NH3 Complexes Containing Multidentate Polypyridyl Ligands

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.