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Modulation of Phenol Oxidation in Cofacial Dyads
Bon Jun Koo1, Michael Huynh1, Robert L Halbach1
1Department of Chemistry and Chemical Biology, Harvard University , 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
Abstract:
The presentation of two phenols on a xanthene backbone is akin to the tyrosine dyad (Y730 and Y731) of ribonucleotide reductase. X-ray crystallography reveals that the two phenol moieties are cofacially disposed at 4.35 Å. Cyclic voltammetry reveals that phenol oxidation is modulated within the dyad, which exhibits a splitting of one-electron waves with the second oxidation of the phenol dyad occurring at larger positive potential than that of a typical phenol. In contrast, a single phenol appended to a xanthene exhibits a two-electron process, consistent with reported oxidation pathways of phenols in acetonitrile. The perturbation of the phenol potential by stacking is reminiscent of a similar effect for guanines stacked within DNA base pairs.
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