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Cover Feature: Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex (Chem. Eur. J. 69/2017)
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.201704491
Subject(s) - rhodium , pincer movement , chemistry , azide , dimer , electrochemistry , intramolecular force , medicinal chemistry , catalysis , photochemistry , polymer chemistry , stereochemistry , electrode , organic chemistry
One‐electron oxidation of a PNP pincer rhodium(I)‐azido complex [Rh(PNP)(N 3 )] leads to selective formation of a rhodium(I)–N 2 complex [Rh(PNP)(N 2 )] + . This complex functions as a catalyst for electrochemical N 3 − oxidation at a milder potential than direct oxidation of N 3 − 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)(N 2 )]. 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. on page 17438.