Revisiting the Electrochemistry of TEMPOH Analogues in Acetonitrile

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.

Automated summary

In this study, the electrochemistry of TEMPOH derivatives in acetonitrile was revisited, revealing much lower oxidation potentials (around 0 V) compared to literature values. Acid/base effects and kinetic studies supported the credibility of these new values, challenging the previously reported 0.7 V oxidation potential discrepancy.