Experimental and computational investigation of the substituent effects on the reduction of Fe3+ by 1,2-dihydroxybenzenes

Authors
Salgado, Pablo; Contreras, David; Mansilla, Héctor D.; Márquez, Katherine; Vidal, Gladys; Cobos, Carlos Jorge; Martire, Daniel Osvaldo
Publication Year
2017
Language
English
Format
article
Status
Published version
Description
This study reports on the kinetics of the early steps that mediate the reactions of substituted 1,2-dihydroxybenzenes (1,2-DHB) with Fe3+. 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 Fe3+ and the 1,2-DHB, which is accompanied by proton loss. The second process involves the inner-sphere electron transfer from the ligand to Fe3+ 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.
Fil: Salgado, Pablo. Universidad de Concepción; Chile
Fil: Contreras, David. Universidad de Concepción; Chile
Fil: Mansilla, Héctor D.. Universidad de Concepción; Chile
Fil: Márquez, Katherine. Universidad de Concepción; Chile
Fil: Vidal, Gladys. Universidad de Concepción; Chile
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Martire, Daniel Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Subject
SIDEROPHORES
IRON(III)
REDUCTION
STOPPED-FLOW
Otras Ciencias Químicas
Ciencias Químicas
CIENCIAS NATURALES Y EXACTAS
Access level
Restricted access
License
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repository
CONICET Digital (CONICET)
Institution
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identifier
oai:ri.conicet.gov.ar:11336/63917