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Electrochemical Properties of Vanadium(III,IV,V)−Salen Complexes in Acetonitrile. Four-Electron Reduction of O_2 by V(III)−Salen

Liu, Zenghe and Anson, Fred C. (2000) Electrochemical Properties of Vanadium(III,IV,V)−Salen Complexes in Acetonitrile. Four-Electron Reduction of O_2 by V(III)−Salen. Inorganic Chemistry, 39 (2). pp. 274-280. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170808-094651903

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Abstract

The coordination chemistry and electrochemistry of complexes of vanadium(III,IV,V) with salen (H_2 salen = N,N‘-ethylenebis(salicylideneamine) were reexamined in an attempt to uncover the origin of puzzling results reported in a previous study (Inorg. Chem. 1994, 33, 1056). Microelectrodes were utilized to allow measurements in the absence of supporting electrolyte. The source of the puzzling results was identified and the modifications required in the previous interpretations are specified. Corrected values of formal potentials and diffusion coefficients are also given. The acid-induced disproportionation of V^(IV)O(salen), as originally proposed by Bonadies et al. (J. Chem. Soc., Chem. Commun. 1986, 1218; Inorg. Chem. 1987, 26, 1218), was largely supported by the present results. The equilibrium constant for this disproportionation reaction was measured. The stoichiometry and kinetics of the reaction between O_2 and the V(III)−salen complex were examined, and a possible mechanism for this four-electron reduction of O_2 is suggested.


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https://doi.org/10.1021/ic990958zDOIArticle
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Additional Information:© 2000 American Chemical Society. Received August 10, 1999. Publication Date (Web): December 18, 1999. This work was supported by the National Science Foundation. Our interest in V(salen) complexes resulted from extensive discussions and collaborations with Prof. Eishun Tsuchida and his group for which we are most grateful.
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Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170808-094651903
Official Citation:Electrochemical Properties of Vanadium(III,IV,V)−Salen Complexes in Acetonitrile. Four-Electron Reduction of O2 by V(III)−Salen Zenghe Liu and Fred C. Anson Inorganic Chemistry 2000 39 (2), 274-280 DOI: 10.1021/ic990958z
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ID Code:79922
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Deposited By: Tony Diaz
Deposited On:09 Aug 2017 19:31
Last Modified:03 Oct 2019 18:25

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