Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
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Publication date
2017-12-11
Authors
Rebreyend, Christophe
Gloaguen, Yann
Lutz, M.
Van Der Vlugt, Jarl Ivar
Siewert, Inke
Schneider, Sven
Bruin, Bas De
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Document Type
Article
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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.
Keywords
dinitrogen complexes, EPR spectroscopy, fuel cells, nitrido, rhodium
Citation
Rebreyend, C, Gloaguen, Y, Lutz, M, Van Der Vlugt, J I, Siewert, I, Schneider, S & Bruin, B D 2017, 'Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex', Chemistry - A European Journal, vol. 23, no. 69, pp. 17438-17443. https://doi.org/10.1002/chem.201702938