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Electron-transfer reactions with unusual activation parameters. Treatment of reactions accompanied by large entropy decreases

Marcus, R. A. and Sutin, N. (1975) Electron-transfer reactions with unusual activation parameters. Treatment of reactions accompanied by large entropy decreases. Inorganic Chemistry, 14 (1). pp. 213-216. ISSN 0020-1669. http://resolver.caltech.edu/CaltechAUTHORS:20150810-163729417

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Abstract

The activation enthalpies for the oxidation of Fe(H_2O)_6^(2+) by poly(pyridine)iron(III) and -ruthenium(III) complexes (reactions 1 and 2, for example) are small or slightly negative. Fe(H_2O)_6^(2+-) + Fe(bipy)_3^(3+) → Fe(H_2O)_6^(3+) + Fe(bipy)_3^(2+) (1) Fe(H_2O)_6^(2+) + Ru(bipy)_3^(3+) → Fe(H_2O)_6^(3+) + Ru(bipy)_3^(2+) (2) This has led to the suggestion that these reactions occur by a "non-Marcus" path which includes at least one distinctive feature not considered in a current outer-sphere electron-transfer model. We wish to point out that small or even negative activation enthalpies are in themselves not necessarily inconsistent with this model and indeed are predicted by it for the systems under consideration.


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http://dx.doi.org/10.1021/ic50143a051DOIArticle
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Additional Information:© 1975 American Chemical Society. Received June 11, 1974. This work was performed under the auspices of the U. S. Atomic Energy Commission and was supported in part by a grant from the National Science Foundation.
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Atomic Energy CommissionUNSPECIFIED
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Record Number:CaltechAUTHORS:20150810-163729417
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150810-163729417
Official Citation:Electron-transfer reactions with unusual activation parameters. Treatment of reactions accompanied by large entropy decreases R. A. Marcus and N. Sutin Inorganic Chemistry 1975 14 (1), 213-216 DOI: 10.1021/ic50143a051
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59377
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:11 Aug 2015 15:50
Last Modified:13 Feb 2019 18:06

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