Two pathways of carbon dioxide catalyzed oxidative coupling of phenol by peroxynitrite

Carbon dioxide catalyzed oxidative coupling of phenol by peroxynitrite occurs by two pathways distinguished by the isomer ratio of 2,2'- to 4,4'-biphenols. As already established, at neutral pH and moderate phenol concentrations, both biphenols are formed in comparable yields by the coupling of two phenoxyl radicals. However, at high pH and phenol concentration, 2,2'-biphenol is the only identified coupled product, and its formation does not involve phenoxyl radicals. Instead, under these conditions, a previously unreported long-lived (t(1/2) approximately 10 s at pH 10 and 1 mM phenol) diamagnetic intermediate with an absorption maximum at 400 nm is observed. This intermediate is formed from phenolate concomitantly with the decay of peroxynitrite and disappears via reaction with phenol [k = (2.4 +/- 0.1) x 10 M(-)(1) s(-)(1) at pH 10.5] to form 2,2'-biphenol. We also find that para-benzoquinone, previously unreported, is formed in up to 5% yield relative to the initial peroxynitrite concentration. The appearance of an absorption band above 500 nm, which might be due to quinhydrone, indicates that hydroquinone is a likely para-benzoquinone precursor. The dependence of para-benzoquinone yields on pH and phenol concentration suggests that its formation is related to the nonradical pathway of 2,2'-biphenol formation. This novel nonradical pathway of 2,2'-biphenol formation might be relevant to the mechanisms of reaction of phenolic antioxidants with peroxynitrite. The existence of two distinct pathways of biphenol formation implies that, apart from a CO(3)(*)(-)/NO(2)(*) radical pair, another reactive intermediate is formed during the carbon dioxide catalyzed decay of peroxynitrite.