Kinetics and Mechanism of Electron Transfer to Manganese(VII) by Fluorene and Its Halogenated Derivatives in Neutral Organic Medium

Abstract

The kinetics of oxidation of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), by permanganate ion in neutral organic medium in the presence of phosphate buffer solution has been investigated at a constant temperature of 25°C. The progresses of the reactions were followed spectrophotometrically. The stoichiometry of the reactions was found to be 3:4 (fluorene: permanganate). The oxidation reactions exhibited a first order dependence in [permanganate] and less than unit order dependences with respect to fluorenes concentrations. Under comparable experimental conditions, the order of the oxidation rate of the fluorene derivatives was: Fl-Cl > Fl > Fl-I > Fl-Br. The final oxidation products of fluorene derivatives were identified by GC/MS, FT-IR and chemical tools as the corresponding ketones (9H-fluorenone derivatives). The proposed oxidation mechanism involves formation of 1:1 intermediate complexes between fluorene derivatives and permanganate ion in pre-equilibrium step. The ratelaw expression was deduced. The reactions constants involved in the different steps of the mechanism were evaluated. The activation parameters associated with the second order rate constants were calculated and discussed.