Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

In bimolecular homolytic substitution reactions type S_H2 between coordinated peroxy radicals [Co(III)]RO₂ and partially hindered bisphenol 4,4'-thiobis-(3-methyl-6-tert-butylphenol) (an antioxidant with commercial name Santonox R) in non-polar medium at room temperature an equilibrium is established between free and Co(III)-coordinated phenoxy radicals. Increasing temperature shifts the equilibrium in favour of the decomplexed free radicals. The complexation-decomplexation process of phenoxy radicals is practically reversible up to 90°C. Polar coordinating solvents (methanol, H₂O, diethyl ether, tetrahydrofurane) displace irreversibly the radicals from the complexes. From their decomposition kinetics at various temperatures activation energy of decomplexation by methanol has been determined (110 ± 8 kJ mol^-1). The displaced free partially hindered phenoxy radicals are not sufficiently stable and undergo subsequent radical transformations (dimerization, intramolecular and intermolecular H-transfer) with effective activation energy about 67 kJ mol^-1.