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Revisiting the Electrochemistry of TEMPOH Analogues in Acetonitrile
Xiao Zhao1, Jin-Dong Yang1, Jin-Pei Cheng1,2
1Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Abstract:
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.
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