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Cobalt(III) Corroles as Electrocatalysts for the Reduction of Dioxygen: Reactivity of a Monocorrole, Biscorroles, and Porphyrin−Corrole Dyads

Kadish, Karl M. and Frémond, Laurent and Ou, Zhongping and Shao, Jianguo and Shi, Chunnian and Anson, Fred C. and Burdet, Fabien and Gros, Claude P. and Barbe, Jean-Michel and Guilard, Roger (2005) Cobalt(III) Corroles as Electrocatalysts for the Reduction of Dioxygen: Reactivity of a Monocorrole, Biscorroles, and Porphyrin−Corrole Dyads. Journal of the American Chemical Society, 127 (15). pp. 5625-5631. ISSN 0002-7863. doi:10.1021/ja0501060.

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Three series of cobalt(III) corroles were tested as catalysts for the electroreduction of dioxygen to water. One was a simple monocorrole represented as (Me_4Ph_5Cor)Co, one a face-to-face biscorrole linked by an anthracene (A), biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or dibenzothiophene (S) bridge, (BCY)Co_2 (with Y = A, B, X, O or S), and one a face-to-face bismacrocyclic complex, (PCY)Co_2, containing a Co(II) porphyrin and a Co(III) corrole also linked by one of the above rigid spacers (Y = A, B, X, or O). Cyclic voltammetry and rotating ring−disk electrode voltammetry were both used to examine the catalytic activity of the cobalt complexes in acid media. The mixed valent Co(II)/Co(III) complexes, (PCY)Co_2, and the biscorrole complexes, (BCY)Co_2, which contain two Co(III) ions in their air-stable forms, all provide a direct four-electron pathway for the reduction of O_2 to H_2O in aqueous acidic electrolyte when adsorbed on a graphite electrode, with the most efficient process being observed in the case of the complexes having an anthracene spacer. A relatively small amount of hydrogen peroxide was detected at the ring electrode in the vicinity of E_(1/2) which was located at 0.47 V vs SCE for (PCA)Co_2 and 0.39 V vs SCE for (BCA)Co_2. The cobalt(III) monocorrole (Me_4Ph_5Cor)Co also catalyzes the electroreduction of dioxygen at E_(1/2) = 0.38 V with the final products being an approximate 50% mixture of H_2O_2 and H_2O.

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Additional Information:© 2005 American Chemical Society. Received 7 January 2005. Published online 26 March 2005. Published in print 1 April 2005. K.M.K. is grateful to the Robert A. Welch Foundation (Grant E-680) for support of this research as is L.K. for a predoctoral fellowship. The Région Bourgogne and CNRS are also acknowledged for financial support and for a BDI fellowship (F.B.).
Funding AgencyGrant Number
Robert A. Welch FoundationE-680
Région BourgogneUNSPECIFIED
Centre National de la Recherche Scientifique (CNRS)UNSPECIFIED
Issue or Number:15
Record Number:CaltechAUTHORS:20170516-072216755
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Official Citation:Cobalt(III) Corroles as Electrocatalysts for the Reduction of Dioxygen:  Reactivity of a Monocorrole, Biscorroles, and Porphyrin−Corrole Dyads Karl M. Kadish, Laurent Frémond, Zhongping Ou, Jianguo Shao, Chunnian Shi, Fred C. Anson, Fabien Burdet, Claude P. Gros, Jean-Michel Barbe, and Roger Guilard Journal of the American Chemical Society 2005 127 (15), 5625-5631 DOI: 10.1021/ja0501060
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77479
Deposited By: Ruth Sustaita
Deposited On:16 May 2017 16:25
Last Modified:15 Nov 2021 17:31

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