Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
Christophe Rebreyend1, Yann Gloaguen1, Martin Lutz2
1Homogeneous and Supramolecular Catalysis van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Amsterdam, The Netherlands.
Abstract:
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.
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