Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenesElectronic supplementary information (ESI) available. See DOI: 10.1039/c7nj01322a

• Main Authors: Salgado, Pablo, Contreras, David, Mansilla, Héctor D, Márquez, Katherine, Vidal, Gladys, Cobos, Carlos J, Mártire, Daniel O
• Format: Article
• Language: English
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/c7nj01322a

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. This study reports on the kinetics of the early steps of the reactions between substituted 1,2-dihydroxybenzenes (1,2-DHB) and Fe 3+ .