An Intramolecular Hydrogen-Shift in a Peroxy Radical at Cryogenic Temperatures: The Reaction of 2-Hydroxyphenyl Radical with O2.

Abstract

Peroxy radical hydrogen-shifts are pivotal elementary reaction steps in the oxidation of small hydrocarbons in autoignition and the lower atmosphere. Although these reactions are typically associated with a substantial barrier, we demonstrate that the [1,5]H-shift in the peroxy species derived from the 2-hydroxyphenyl radical 1 is so facile that it even proceeds rapidly in an argon matrix at 35 K through a proton-coupled electron transfer mechanism. Hydrogen-bound complexes of o-benzoquinone are identified as the main reaction products by infrared spectroscopy although their formation through O-O bond scission is hampered by a barrier of 11.9 kcal mol-1 at the ROCCSD(T)/cc-pVTZ/UB3LYP/6-311G(d,p) level of theory.