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

One‐electron oxidation of the rhodium(I) azido complex [Rh(N(3))(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(N(2))(PNP)](+) (9 (+)). Intere...

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Detalles Bibliográficos
Autores principales: Rebreyend, Christophe, Gloaguen, Yann, Lutz, Martin, van der Vlugt, Jarl Ivar, Siewert, Inke, Schneider, Sven, de Bruin, Bas
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5765409/
https://www.ncbi.nlm.nih.gov/pubmed/28898478
http://dx.doi.org/10.1002/chem.201702938
Descripción
Sumario:One‐electron oxidation of the rhodium(I) azido complex [Rh(N(3))(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(N(2))(PNP)](+) (9 (+)). Interestingly, complex 5 also acts as a catalyst for electrochemical N(3) (−) oxidation (E (p)≈−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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