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Catalysis of the Electro-Oxidation of Carbon Monoxide by Cobalt Octaethylporphyrin

Shi, Chunnian and Anson, Fred C. (2001) Catalysis of the Electro-Oxidation of Carbon Monoxide by Cobalt Octaethylporphyrin. Inorganic Chemistry, 40 (23). pp. 5829-5833. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170315-150552429

[img] PDF (Two figures showing cyclic voltammograms for Co(OEP) in the presence of pyrazine or imidazole with and without CO and the variation in the formal potential of the Co(III/II) couple with the concentration of imidazole) - Supplemental Material
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Abstract

The electro-oxidation of cobalt (II) octaethylporphyrin adsorbed on graphite electrodes, Co^(II)(OEP)_(ads') to Co^(III)(OEP) ^+_(ads), in the presence of aqueous solutions of CO leads to catalytic oxidation of CO to CO_2. No such oxidation occurs with Co^(II)(OEP) and CO dissolved in nonaqueous solvents. Coordination of the CO to Co^(III)(OEP)^+ is the first step in the catalytic mechanism. Nucleophilic attack on the coordinated CO by H_2O is the probable rate-limiting step in the catalytic oxidation. A pseudo first-order rate constant of 0.3 s^(-1) was estimated for this reaction.


Item Type:Article
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http://dx.doi.org/10.1021/ic010530bDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic010530bPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic010530bPublisherSupporting Information
Additional Information:© 2001 American Chemical Society. Received May 21, 2001. Publication Date (Web): September 26, 2001. This work was supported by the National Science Foundation. We are grateful to Prof. Karl Kadish for calling our attention to the reaction between Co(III) porphyrins and CO.
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Issue or Number:23
Record Number:CaltechAUTHORS:20170315-150552429
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170315-150552429
Official Citation:Catalysis of the Electro-Oxidation of Carbon Monoxide by Cobalt Octaethylporphyrin Chunnian Shi and Fred C. Anson Inorganic Chemistry 2001 40 (23), 5829-5833 DOI: 10.1021/ic010530b
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75154
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 Mar 2017 17:05
Last Modified:03 Oct 2019 16:47

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