Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1, 2-dihydroxybenzenes. (2nd October 2017)

• Record Type: Journal Article
• Authors: Salgado, Pablo; Contreras, David; Mansilla, Héctor D.; Márquez, Katherine; Vidal, Gladys; Cobos, Carlos J.; Mártire, Daniel O.
• Is Part Of: New journal of chemistry. Volume 41:Number 21(2017)
• Page Start: 12685
• Page End: 12693
• Publication Date: 2017-10-02
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c7nj01322a
• Languages: English
• ISSNs: 1144-0546

Abstract

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