Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH4 functionalization

Abstract

The roles of unforgiving H₂SO₄ solvent in CH₄ activation with molecular catalysts have not been experimentally well-illustrated despite computational predictions. Here, we provide experimental evidence that metal-bound bisulfate ligand introduced by H₂SO₄ solvent is redox-active in vanadium-based electrocatalytic CH₄ activation discovered recently. Replacing one of the two terminal bisulfate ligands with redox-inert dihydrogen phosphate in the pre-catalyst vanadium (V)-oxo dimer completely quenches its activity towards CH₄, which may inspire environmentally benign catalysis with minimal use of H₂SO₄.