Chromium(III) and indium(III) 3,6-di-tert-butyl-o-semiquinolate complexes as redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes

Abstract

The electrochemical oxidation of the chromium(III) and indium(III) complexes with 3,6-di-tert-butyl-o-semiquinolate leading to the formation of active monocationic species is studied by cyclic voltammetry. The reactions of the latter with hydrogen sulfide generate the radical cation of H₂S, whose fragmentation affords the proton and thiyl radical. These complexes are proposed for the first time as redox mediators for the one-pot thiolation of inert cycloalkanes C₆–C₈, which decreases the activation energy of hydrogen sulfide compared to that for direct electrochemical oxidation. The major products of cycloalkane functionalization involving H₂S are thiols and organic di- and trisulfides. The yield of the synthesized compounds depends on the type of the mediator: the chromium(III) complex exhibits the highest efficiency in the electrocatalytic transformations.