Generation of radical species in surface reactions of chlorohydrocarbons and chlorocarbons with fluorinated gallium(III) oxide or indium(III) oxide

Abstract

The reactions of C₁ and C₂ chlorohydrocarbons and chlorocarbons have been studied with the Lewis acid catalysts fluorinated gallium(III) oxide and fluorinated indium(III) oxide, respectively. Product analysis shows chlorine-for-fluorine exchange reactions together with the formation of 2-methylpropane and its chlorinated analogues 2-chloromethyl-1,3-dichloropropane and 2-chloromethyl-1,2,3-trichloropropane. Reactivities of the chlorohydrocarbon probe molecules show fluorinated gallium(III) oxide to be a stronger Lewis acid than fluorinated indium(III) oxide. The formation of the symmetrical butyl compounds is consistent with the generation of surface radical species and is also consistent with a 1,2-migration mechanism operating within radical moieties at the Lewis acid surface.