Kinetics and Mechanism of Oxidation Reactions of Porphyrin−Iron(IV)−Oxo Intermediates

The kinetics of the reactions of three porphyrin-iron(IV)-oxo derivatives with alkenes and benzylic alcohols were measured. The iron-oxo systems studied were 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (2a), 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (2b), and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin-iron(IV)-oxo (2c). Species 2 were stable for hours at room temperature as dilute solutions in acetonitrile and reacted hundreds to thousands of times faster in the presence of high concentrations of substrates. Typical second-order rate constants determined from pseudo-first-order kinetic studies are 1-2 x 10(-2) M(-1) s(-1) for reactions with styrene and 3 x 10(-2) M(-1) s(-1) for reactions with benzyl alcohol. The reactivity order for the iron-oxo species was 2a > 2b > 2c, which is inverted from that expected on the basis of the electron demand of the porphyrin macrocycles, and the oxidation reaction was suppressed when excess porphyrin-iron(III) complex was added to reaction mixtures. These observations indicate that the reactions involve disproportionation of the iron(IV)-oxo species 2 to give an iron(III) species and a more highly oxidized iron species, presumed to be an iron(IV)-oxo porphyrin radical cation, that is the true oxidant in the reactions. Analyses of the kinetics of oxidations of a series of para-substituted benzylic alcohols with Hammett sigma+ -substituent constants and with a dual-parameter method developed by Jiang (Jiang, X. K. Acc. Chem. Res. 1997, 30, 283) indicated that considerable positive charge developed on the benzylic carbons in the oxidation reactions, as expected for electrophilic oxidants, and also that substantial radical character developed on the benzyl carbon in the transition states.