Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH 4 functionalization.

The roles of unforgiving H 2 SO 4 solvent in CH 4 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 H 2 SO 4 solvent is redox-active in vanadium-based electrocatalytic CH 4 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 CH 4 , which may inspire environmentally benign catalysis with minimal use of H 2 SO 4 .