Serviços Personalizados
Journal
Artigo
Indicadores
- Citado por SciELO
- Acessos
Links relacionados
- Similares em SciELO
Compartilhar
Journal of the Mexican Chemical Society
versão impressa ISSN 1870-249X
Resumo
SUBRAMANIAM, Perumal; VANITHA, Thangadurai; KODISPATHI, Thiruttimuthu e SHANMUGA SUNDARI, Chandra Raj. Role of Iron(III)-salen Chloride as Oxidizing Agent with Thiodiglycolic Acid: The Effect of Axial Ligands. J. Mex. Chem. Soc [online]. 2014, vol.58, n.2, pp.211-217. ISSN 1870-249X.
The sulfoxidation of thiodiglycolic acid with iron(III)-salen chloride, which acts as an oxidizing agent without any terminal oxidant, in 50% aqueous acetonitrile medium has been studied. A substantial red shift in the λmaxvalue of FeIII-salen was observed in aqueous medium. The spectrophotometric kinetic study indicates that [FeIII(salen)]+ is the active oxidizing species and the reaction follows Michaelis-Menten kinetics with respect to the substrate. The rate of the reaction is highly sensitive to the medium. A reaction mechanism involving electron transfer from sulfur atom of thiodiglycolic acid to the central iron atom of [FeIII(salen)]+ is proposed. The presence of nitrogenous bases like pyridine, imidazole and 1-methylimidazole shows a retarding effect on the reaction rate. This can be explained on the basis of binding of these ligands to the coordination sphere of [FeIII(salen)]+ prior to the reaction with the substrate. The observed order of reactivity, pyridine > 1-methylimidazole > imidazole, is in accordance with the inverse of π-donating ability of nitrogen bases.
Palavras-chave : Thiodiglycolic acid; Iron(III)-salen; Nitrogenous bases; Michaelis-Menten kinetics; Sulfoxidation.