Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex

One‐electron oxidation of the rhodium(I) azido complex [Rh(N3)(PNP)] (5), bearing the neutral, pyridine‐based PNP ligand 2,6‐bis(di‐tert‐butylphosphinomethyl)pyridine, leads to instantaneous and selective formation of the mononuclear rhodium(I) dinitrogen complex [Rh(N2)(PNP)]+ (9+). Interestingly, complex 5 also acts as a catalyst for electrochemical N3− oxidation (Ep≈−0.23 V vs. Fc+/0) in the presence of excess azide. This is of potential relevance for the design of azide‐based and direct ammonia fuel cells, expelling only harmless dinitrogen as an exhaust gas. Electrocatalytic azide oxidation: One‐electron oxidation of the rhodium(I) azido complex [Rh(N3)(PNP)], bearing the neutral, pyridine‐based PNP ligand 2,6‐bis(di‐tert‐butyl phosphine methyl)pyridine, leads to instantaneous and selective formation of the mononuclear rhodium(I) dinitrogen complex [Rh(N2)(PNP)]+.