Modulation of Phenol Oxidation in Cofacial Dyads
Name
Stubbe_Modulation of Phenol Oxidation.pdf
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1.39 MB
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Author(s)
Koo, Bon Jun
Huynh, Michael
Halbach, Robert L.
Stubbe, JoAnne
Nocera, Daniel G.
Date Issued
August 2015
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Koo, Bon Jun et al. “Modulation of Phenol Oxidation in Cofacial Dyads.” Journal of the American Chemical Society 137.37 (2015): 11860–11863. © 2015 American Chemical Society
Version
Author's final manuscript
Abstract
The presentation of two phenols on a xanthene backbone is akin to the tyrosine dyad (Y[subscript 730] and Y[subscript 731]) 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
http://dx.doi.org/10.1021/jacs.5b05955
