Aquachlororuthenium(III) catalysis in the oxidation of substituted 4-oxo-4-arylbutanoic acids by bromate in acid medium: a kinetic and mechanistic study and validity of linear free-energy relationships

Abstract

Ru(III) acts an efficient catalyst in the oxidation of substituted 4-oxo-4-arylbutanoic acids (4-oxo acids) by bromate in sulfuric acid medium, giving the corresponding benzoic acids in quantitative yields. The reaction shows first-order dependence in both [bromate] and [H 2 SO 4 ], and a non-linear dependence on both [oxo acid] and [catalyst]. Changing solvent from H 2 O to D 2 O increases the rate. The rate is not affected by ionic strength but decreases with increase in dielectric constant of the medium. Electron-releasing substituents in the phenyl ring of the substrate greatly accelerate the rate, whereas the retardation by electron-withdrawing substituents, though perceptible, is small. The linear free-energy relationship is characterized by smooth curves in Hammett plots of log k versus r; however, linear plots are obtained with excellent correlation coefficients at all the studied temperatures, when Brown's r ? values are used. The reaction constant is negative and decreases with increase in temperature. From the intersection of the lines in the Hammett and Arrhenius plots, the isokinetic relationship is evaluated. A mechanism involving a cyclic oxidant-substrate-catalyst ternary complex is proposed, in which both C-C bond-breaking and C-O bond formation are involved, and the oxidation state of Ru(III) remains unchanged. A rate law explaining all the kinetic results has been derived and verified. The reaction is an example of neighboring group participation in intramolecular catalysis and is potentially useful for the synthesis of substituted benzoic acids.

Interdependence of the Hammett and isokinetic relationships: a numerical simulation approach

“…It can be observed that the deviations of the enthalpy increased linearly with those of the entropy, the slope (T) being dimensionally a temperature. This and other statistical parameters were systematically analyzed for 10 homologous reaction series searched in the chemical literature [59][60][61][62][63][64]. Since it has been demonstrated [35][36][37] that the random errors of the activation enthalpy are directly proportional to those of the entropy, according to the equation:…”