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Publication Type
Journal Article
Author, Analytic
Copeland, Eddia P.,; Kahwa, Ishenkumba A.; Mague, Joel T.; McPherson, Gary L.
Author Affiliation, Ana.
Chemistry; Faculty of Pure and Applied Sciences
Article Title
Novel mixed-valence vanadium (iv/v) molecule exhibiting unusual electron delocalization over the [V2O3]3+
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Journal Title
Journal of the Chemical Society. Dalton Transactions
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Reprint Status
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Date of Publication
1997
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Issue ID
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Page(s)
2849-2852
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Notes
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Abstract
Condensation of metholic salicylaldehyde and triethylenetetramine in the presence of vanadyl sulfate (VOSO4) in a 3:1:2 mole ratio respectively yielded a new dinuclear mixed-valence vanadium (IV/V) Schiff-base molecule [V2O3L1]1. The crystal structure of 1 revealed the molecule to be in a bent conformation with the vanadyl units (VO) cis to each other and to the oxo VOV bridge. The V(-O)(-phenolate) V bridge is marginally asymmetric [V-Ooxo1.811(2) and 1.84(2), V-Ophenolate 2.180(2) and 2.203(2) ]. Normally, these geometrical properties are considered unfavourable for electron delocalization over the oxo V-O-V bridge. However, remarkably, the paramagnetic molecule 1 ( = 1.73B) features an unpaired electron delocalized over the vanadyl centres. The EPR spectra of frozen solutions and polycrystalline samples of 1 revealed extensive vanadium-vanadium interactions which are most evident in the 15-line solution EPR spectrum in dimethyl sulfoxide or acetonitrile at room temperature. Cyclic voltammograms showed a single electron loss at E = 0.486 V (with respect to the standard calomel electrode)....
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