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Electrochemical Assessment of the Stability of [Os(NH_3)_5(OH_2)]^(2+) in Aqueous Solutions

Shi, Chunnian and Anson, Fred C. (1997) Electrochemical Assessment of the Stability of [Os(NH_3)_5(OH_2)]^(2+) in Aqueous Solutions. Inorganic Chemistry, 36 (12). pp. 2682-2687. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20180529-110854891

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Abstract

The [Os(NH_3)_5(OH_2)]^(2+) complex in aqueous acid has been widely regarded as short-lived on the basis of results reported in an early pioneering electrochemical study.1 More recently, a much longer-lived Os(II) species generated by reduction of [Os(NH)3))5(OH)2)]^(3+) but of uncertain composition has been reported. In the present study the lifetime of [Os(NH_3)_5(OH_2)]^(2+) in aqueous acid was determined by steady-state voltammetry at a carbon microelectrode and by comparing experimental with simulated cyclic voltammograms obtained for solutions of [Os(NH_3)_5(OH_2)]^(3+). Rate constants for the oxidation of [Os(NH_3)_5(OH_2)]^(2+) by H^+, CH_3COOH (HA), and H_2O were evaluated as k_H = 17 M^(-1) s^(-1), k_(HA) = 1.2 M^(-1) s^(-1), and k_(H_2O) = 4.1 × 10^(-4) s^(-1). These values are shown to be compatible with the data in ref 1 and come close to accounting for the long-lived species described in ref 6 which may be [Os(NH_3)_5(OH_2)]^(2+) itself. A revised value of 4.85 was measured for the pKA of [Os(NH_3)_5(OH_2)]^(3+). Adsorption of an Os complex on the surface of mercury, but not glassy carbon, electrodes is shown to enhance greatly the rate with which protons undergo direct electroreduction.


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https://dx.doi.org/10.1021/ic961522bDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ic961522bPublisherSupporting Information
Additional Information:© 1997 American Chemical Society. Received December 27, 1996. This work was supported by the National Science Foundation. Helpful suggestions and comments from Prof. W. D. Harman were greatly appreciated. Dr. Minglian Shi's assistance in the preparation and use of the microelectrode was invaluable.
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Issue or Number:12
Record Number:CaltechAUTHORS:20180529-110854891
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180529-110854891
Official Citation:Electrochemical Assessment of the Stability of [Os(NH3)5(OH2)]2+ in Aqueous Solutions Chunnian Shi and Fred C. Anson Inorganic Chemistry 1997 36 (12), 2682-2687 DOI: 10.1021/ic961522b
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86663
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:29 May 2018 18:18
Last Modified:03 Oct 2019 19:46

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