Experimental and computational investigation of the substituent effects on the reduction of Fe 3+ by 1,2-dihydroxybenzenes

This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe 3+ . The rate constants of the three processes identified by means of the stopped-flow technique are affected by the electron-withdrawing or electron-donating abili...

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Bibliographic Details
Published in:New journal of chemistry 2017, Vol.41 (21), p.12685-12693
Main Authors: Salgado, Pablo, Contreras, David, Mansilla, Héctor D., Márquez, Katherine, Vidal, Gladys, Cobos, Carlos J., Mártire, Daniel O.
Format: Article
Language:English
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Summary:This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe 3+ . The rate constants of the three processes identified by means of the stopped-flow technique are affected by the electron-withdrawing or electron-donating abilities of the substituent. The fastest process is assigned to the formation of a 1 : 1 complex between Fe 3+ and the 1,2-DHB, which is accompanied by proton loss. The second process involves the inner-sphere electron transfer from the ligand to Fe 3+ and the slowest step is related to the deprotonation of one of the oxygen atoms bonded to the metal. A reaction mechanism is proposed on the basis of the experimental data and density functional theory (DFT) calculations on mono- and bidentate species with different degrees of protonation.
ISSN:1144-0546
1369-9261
DOI:10.1039/C7NJ01322A