Mechanistic Dichotomy in Proton-Coupled Electron-Transfer Reactions of Phenols with a Copper Superoxide Complex.

ABSTRACT: The kinetics and mechanism(s) of the reactions of [K(Krypt)][LCuO₂] (Krypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, L = a bis(arylcarboxamido)pyridine ligand) with 2,2,6,6-tetramethylpiperdine- N-hydroxide (TEMPOH) and the para-substituted phenols ^XArOH (X = para substituent NO₂, CF₃, Cl, H, Me, ^tBu, OMe, or NMe₂) at low temperatures were studied. The reaction with TEMPOH occurs rapidly ( k = 35.4 ± 0.3 M^-1 s^-1) by second-order kinetics to yield TEMPO^• and [LCuOOH]^- on the basis of electron paramagnetic resonance spectroscopy, the production of H₂O₂ upon treatment with protic acid, and independent preparation from reaction of [NBu₄

SUBMITTER: Bailey WD 

PROVIDER: S-EPMC6584633 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature