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Schiff Base Complexes of Vanadium(III, IV, V) as Catalysts for the Electroreduction of O_2 to H_2O in Acetonitrile

Liu, Zenghe and Anson, Fred C. (2001) Schiff Base Complexes of Vanadium(III, IV, V) as Catalysts for the Electroreduction of O_2 to H_2O in Acetonitrile. Inorganic Chemistry, 40 (6). pp. 1329-1333. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170424-125035745

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Abstract

Fifteen Schiff base ligands were synthesized and used to form complexes with vanadium in oxidation states III, IV, and V. Electrochemical and spectral characteristics of the complexes were evaluated and compared. In acidified solutions in acetonitrile the vanadium(IV) complexes undergo reversible disproportionation to form V(III) and V(V) complexes. With several of the ligands the V(III) complexes are much more stable in the presence of acid than is the previously studied complex with salen, an unelaborated Schiff base ligand (H_2 salen = N,N‘-ethylenebis(salicylideneamine)). Equilibrium constants for the disproportionation were evaluated. The vanadium(III) complexes reduce dioxygen to form two oxo ligands. The reaction is stoichiometric in the absence of acid, and second-order rate constants were evaluated. In the presence of acid some of the complexes investigated participate in a catalytic electroreduction of dioxygen.


Item Type:Article
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http://dx.doi.org/10.1021/ic0010407DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic0010407PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic0010407PublisherSupporting Information
Additional Information:© 2001 American Chemical Society. Received 13 September 2000. Published online 13 February 2001. Published in print 1 March 2001. This work was supported by the National Science Foundation. Z.L. was the grateful recipient of a 2000 Energy Research Summer Fellowship of The Electrochemical Society.
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The Electrochemical SocietyUNSPECIFIED
Issue or Number:6
Record Number:CaltechAUTHORS:20170424-125035745
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170424-125035745
Official Citation:Schiff Base Complexes of Vanadium(III, IV, V) as Catalysts for the Electroreduction of O2 to H2O in Acetonitrile Zenghe Liu and Fred C. Anson Inorganic Chemistry 2001 40 (6), 1329-1333 DOI: 10.1021/ic0010407
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76858
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:24 Apr 2017 22:35
Last Modified:03 Oct 2019 17:50

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