Author： Bhattacharyya Jhimli Mukhopadhyay Subrata
Publisher： Springer Publishing Company
ISSN： 0340-4285
Source： Transition Metal Chemistry, Vol.31, Iss.2, 2006-03, pp. : 256-261
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Abstract
The kinetics of oxidation of hydroquinone (H2Q) by a -oxo-bridged diiron(III,III) complex, Fe2(-O)(phen)4(H2O)2]4+ (1) has been investigated in aqueous media at 25.0 °C in presence of an excess of 1,10-phenanthroline (phen). The overall redox rate increases with increase in [H+]. The title complex (1) and its conjugate bases, [Fe2(-O)(phen)4(OH)2]3+(2) and [Fe2(-O)(phen)4(OH)2]2+ (3), participate in the reaction with H2Q as the only kinetically reactive reducing species. Rate constants (in dm3 mol−1 s−1) for the parallel reactions (1) + H2Q → Products, (2) + H2Q → Products and that for (3) + H2Q → Products are, respectively, 500 ± 40, 100 ± 6 and 30 ± 2. Substantial rate retardation in D2O media in comparison to that in H2O media suggests that electron transfer is coupled with proton movements in the rate-determining step.
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