5 years ago

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

Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
Bas de Bruin, Sven Schneider, Inke Siewert, Christophe Rebreyend, Jarl Ivar van der Vlugt, Martin Lutz, Yann Gloaguen
One-electron oxidation of a PNP pincer rhodium(I)-azido complex [Rh(PNP)(N3)] leads to selective formation of a rhodium(I)–N2 complex [Rh(PNP)(N2)]+. This complex functions as a catalyst for electrochemical N3− oxidation at a milder potential than direct oxidation of N3− at a Pt electrode. The mechanism includes dimerisation of the rhodium(II)–azido intermediate followed by rapid fragmentation of the azido-bridged dimer to produce the first 0.5 equivalents of [Rh(PNP)(N2)]. A second 0.5 equivalents is formed more slowly, most likely via intramolecular azide-to-nitride attack. More information can be found in the Communication by S. Schneider, B. de Bruin et al. (DOI: 10.1002/chem.201702938).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201704491

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