Activation of C–H bonds of normal alkanes in sulfuric acid solutions of Mn(III)/Mn(II)

One of the most important directions of establishing the mechanisms of activation of C–H bonds, both in saturated and aromatic hydrocarbons in aqueous and sulfuric acid solutions of oxidants, metal complexes and radicals, is to study the kinetics of reactions and the influence of temperature, environment, nature of reagents, etc. The study of mechanisms is important for the development of technologies for processing hydrocarbons into products with high added value. In this work, to determine the nature of limiting stages and mechanisms of reactions of one group of saturated hydrocarbons, normal alkanes, we use the dependences of substrate selectivity (relative rate constants) on their characteristics: ionization potentials, energy and number of primary and secondary C–H bonds. To determine the nature of the limiting stages of reactions of normal alkanes, the correlations between the logarithms of substrate selectivity of alkanes reactions in H2SO4 solutions with one of the most active manganese(III) ions and molecule properties or C–H bond type were studied by the method of correlation analysis. Comparison of the obtained results with quantum-chemically calculated enthalpy changes of different possible variants of the course of this elementary reaction allowed to clarify the mechanism and propose tests to perform the mechanism of the slow limiting stage. It is shown that for alkanes (ethane, pentane, hexane, heptane, octane) the linear dependence with the ionization potential is most accurately performed, the least accurate is the correlation with the number of secondary C–H bonds, which indicates the electron abstraction in the slow limiting stage. For the shorter pentane – octane series, correlation dependences on both the number of secondary C–H bonds and the ionization potentials are performed with almost equal accuracy, which makes it impossible to establish the nature of the slow stage. The results of quantum-chemical calculations of hexane reactions in Mn(III)/Mn(II)–H2SO4 solutions showed that the most favorable are the electron abstraction by manganese(III) and subsequent proton transfer or homolysis of the C–H bond under the action of bisulfate radical, which is likely formed in the oxidation of sulfuric acid by manganese(III).