posted on 2022-12-27, 15:04authored byXiao Zhao, Jin-Dong Yang, Jin-Pei Cheng
Hydroxylamines, represented by 1-hydroxy-2,2,6,6-tetramethylpiperidine
(TEMPOH), are widely involved as active species in various chemical
and electrochemical oxidations. The electrochemical behavior of TEMPOH
is crucial to understanding the mechanisms of TEMPO-mediated redox
sequences. However, compared to abundant studies on TEMPOH electrochemistry
in aqueous solutions, the sole value of its oxidation potential Eox(TEMPOH) in organic solutions was reported
to be 0.7 V (vs Fc in acetonitrile), seemingly conflicting with experimentally
observed facile oxidation of TEMPOH. Herein, the electrochemistry
of TEMPOH derivatives in acetonitrile was revisited, featuring much
smaller oxidation potentials (about 0 V) than literature ones. Acid/base
effects and kinetic studies lent credibility to these new values.
Such a 0.7 V energy discrepancy impelled us to review the thermodynamic
properties and oxidation mechanisms of TEMPOH deduced from the old
value.