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

Open Access
Authors
Publication date 11-12-2017
Journal Chemistry - A European Journal
Volume | Issue number 23 | 69
Pages (from-to) 17438-17443
Number of pages 6
Organisations
  • Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
  • Faculty of Science (FNWI)
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≈0.23V 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.
Document type Article
Language English
Related dataset CCDC 1479725: Experimental Crystal Structure Determination CCDC 1555543: Experimental Crystal Structure Determination CCDC 1479724: Experimental Crystal Structure Determination
Published at https://doi.org/10.1002/chem.201702938
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