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Comparison of the catalytic reduction of oxygen by [5,10,15,20-tetrakis((pentaammineruthenio(II)-4-pyridyl)porphyrinato]cobalt(II) in solution and on graphite electrode surfaces

Shi, Chunnian and Anson, Fred C. (1995) Comparison of the catalytic reduction of oxygen by [5,10,15,20-tetrakis((pentaammineruthenio(II)-4-pyridyl)porphyrinato]cobalt(II) in solution and on graphite electrode surfaces. Inorganic Chemistry, 34 (18). pp. 4554-4561. ISSN 0020-1669. doi:10.1021/ic00122a010. https://resolver.caltech.edu/CaltechAUTHORS:20180801-112457194

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Abstract

The [5, 10, 15,20-tetrakis((pentaammineruthenio(II))-4-pyridylporphinato ]cobalt(II) complex that catalyzes the fourelectron reduction of O_2 at graphite electrode surfaces on which it has been assembled has now been prepared in homogeneous solution. The preparative procedure for the catalyst is described, and the kinetics of its catalysis of the reduction of O_2 by chemical reductants in homogeneous solution are reported. In solution, only twoelectron reductions of O_2 are obtained and the rate of intramolecular electron-transfer from the four Ru(NH_3)_(5-)py^(2+) centers on the periphery of the catalyst molecule to an O_2 molecule coordinated to the Co(II) center in the porphyrin ring is shown to be quite slow. Possible reasons for the contrasting mechanistic behavior of the catalyst in solution and on graphite electrodes are suggested.


Item Type:Article
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https://doi.org/10.1021/ic00122a010DOIArticle
Additional Information:© 1995 American Chemical Society. Received April 14, 1995. This work was supported by the National Science Foundation. Dr. Beat Steiger was a source of continuing, reliable, and stimulating advice. We are most grateful to Prof. James Espenson for insightful comments and assistance with implementation of the Kinsim program.
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Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics9083
Issue or Number:18
DOI:10.1021/ic00122a010
Record Number:CaltechAUTHORS:20180801-112457194
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180801-112457194
Official Citation:Comparison of the catalytic reduction of oxygen by [5,10,15,20-tetrakis((pentaammineruthenio(II)-4-pyridyl)porphyrinato]cobalt(II) in solution and on graphite electrode surfaces. Chunnian Shi and Fred C. Anson. Inorganic Chemistry 1995 34 (18), 4554-4561. DOI: 10.1021/ic00122a010
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88442
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:01 Aug 2018 19:01
Last Modified:16 Nov 2021 00:26

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