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Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
Author(s) -
Rebreyend Christophe,
Gloaguen Yann,
Lutz Martin,
van der Vlugt Jarl Ivar,
Siewert Inke,
Schneider Sven,
de Bruin Bas
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702938
Subject(s) - azide , pincer movement , rhodium , chemistry , pyridine , catalysis , ammonia , electrochemistry , ligand (biochemistry) , medicinal chemistry , redox , platinum , pincer ligand , combinatorial chemistry , photochemistry , inorganic chemistry , organic chemistry , electrode , receptor , biochemistry
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.