Kinetics of Oxidation of Aromatic Hydrocarbons and Tetrahydrofuran by trans-Dioxoruthenium(VI) Complexes

Article abstract of DOI:10.1039/DT9910003277

The kinetics of oxidation of aromatic hydrocarbons and tetrahydrofuran by trans-VILO2>²⁺ 1 = 6,7,14,15,16,17,18,19-octahydro-14,18-dimethyl-13H-dibenzo<1,4,8,12>dioxadiazacyclopentadecine, L² = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)propylenediamine and L³ = meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetraazabicyclo<11.3.1>heptadeca-1(17),13,15-triene> has been studied.In acetonitrile the second-order rate constants follow the order: toluene < ethylbenzene < cumene.The kinetic isotope effects for the oxidation of ethylbenzene by trans-²⁺ (L = L¹ or L²) are 16 and 12:1 respectively.In the oxidation of tetrahydrofuran by trans-1O2>²⁺, k₂ was found to be 0.170 mol^-1 dm³ s^-1 at 298 K with a measured kinetic isotope effect of 20:1.A linear correlation between log(rate constant) and E⁰(Ru^VI-Ru^IV) for the oxidation of tetrahydrofuran has been observed.The activation parameters for the oxidation reactions have also be determined.A hydrogen-atom abstraction mechanism is suggested for the oxidation of C-H bonds by trans-dioxoruthenium(VI) complexes.

Full text of DOI:10.1039/DT9910003277

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