Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.
The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay.
Department of Chemistry "G. Ciamician", University of Bologna, Via S. Giacomo 11, 40126, Bologna, Italy. riccardo.amorati@unibo.it.
Riccardo
0000-0002-6417-9957
R
Amorati
Department of Chemistry "G. Ciamician", University of Bologna, Via S. Giacomo 11, 40126, Bologna, Italy.
Andrea
A
Baschieri
Department of Chemistry "G. Ciamician", University of Bologna, Via S. Giacomo 11, 40126, Bologna, Italy.
Gloria
G
Morroni
Department of Chemistry "G. Ciamician", University of Bologna, Via S. Giacomo 11, 40126, Bologna, Italy.
Rossana
R
Gambino
Department of Chemistry "G. Ciamician", University of Bologna, Via S. Giacomo 11, 40126, Bologna, Italy. luca.valgimigli@unibo.it.
Luca
0000-0003-2229-1075
L
Valgimigli
antioxidants; kinetics; proton inventory; radical reactions; reaction mechanisms