Mechanistic aspects of the reduction of ruthenium(III) catalyzed |
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Authors: | Mallikarjuna I. Hiremath Sharanappa T. Nandibewoor |
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Affiliation: | (1) P.G. Department of Studies in Chemistry, Karnatak University, Dharwad, 580003, India |
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Abstract: | The kinetics of RuIII catalyzed reduction of hexacyanoferrate(III) [Fe(CN)6]3–, by atenolol in alkaline medium at constant ionic strength (0.80 mol dm–3) has been studied spectrophotometrically, using a rapid kinetic accessory. The reaction between atenolol and [Fe(CN)6]3– in alkaline medium exhibits 1:2 stoichiometry [atenolol:Fe(CN)63–]. The reaction showed first order kinetics in [Fe(CN)6]3– concentration and apparent less than unit order dependence, each in atenolol and alkali concentrations. Effect of added products, ionic strength and dielectric constant of the reaction medium have been investigated. A retarding effect was observed by one of the products i.e., hexacyanoferrate(II). The main products were identified by i.r., n.m.r., fluorimetric and mass spectral studies. A mechanism involving the formation of a complex between the atenolol and the hydroxylated species of ruthenium(III) has been proposed. The active species of oxidant and catalyst were [Fe(CN)6]3–and [Ru (H2O)5OH]2+, respectively. The reaction constants involved in the mechanism were evaluated. The activation parameters were computed with respect to the slow step of the mechanism, and discussed. |
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