Electrocatalytic Oxidation of Ammonia by (Salen)ruthenium(III) Ammine Complexes: Direct Evidence for a Ruthenium(VI) Nitrido Active Intermediate

The electrocatalytic oxidation of ammonia using molecular catalysts has attracted much attention recently due to its potential for fuel cell applications. In this study, we report the electrocatalytic ammonia oxidation (AO) by [Ru^III(salchda)(NH₃)(CH₃CN)]⁺ (<b>RuNH</b>_<b>3</b>, salchda = <i>N,N</i>'-bis(salicylidene)-<i>o</i>-cyclohexyldiamine dianion) and its bromo derivative. Controlled potential electrolysis at 0.65 V versus Fc^+/0 for 3.2 h of a solution of <b>RuNH</b>_<b>3</b> and NH₃ in CH₃CN produced N₂ with a TON of 26 and Faradaic efficiency (FE) close to 100%. The TON was increased to 79 and 147 when electrolysis was carried out at 0.7 and 0.80 V vs Fc^+/0, respectively, with FE maintained at >99%, which are the highest among molecular ruthenium catalysts. An active intermediate was detected and shown to be the corresponding ruthenium(VI) nitrido complex [Ru^VI(salchda)(N)]⁺ (<b>RuN</b>) by direct comparison with an authentic sample of <b>RuN</b>, which we have previously synthesized and fully characterized. Direct kinetic studies on the oxidation of NH₃ to N₂ have also been carried out and the results are consistent with parallel electrophilic attack of NH₃ by <b>RuN</b> and bimolecular N···N coupling of <b>RuN</b> to produce N₂. DFT calculations have also been performed to support the proposed mechanism.