Electrophilic
high-valent metal ions are potent intermediates for
the catalytic functionalization of methane, but in many cases, their
high redox potentials make these intermediates difficult or impossible
to access using mild stoichiometric oxidants derived from O<sub>2</sub>. Herein, we establish electrochemical oxidation as a versatile new
strategy for accessing high-valent methane monofunctionalization catalysts.
We provide evidence for the electrochemical oxidation of simple PdSO<sub>4</sub> in concentrated sulfuric acid electrolytes to generate a
putative Pd<sub>2</sub><sup>III,III</sup> species in an all-oxidic
ligand field. This electrogenerated high-valent Pd complex rapidly
activates methane with a low barrier of 25.9 (±2.6) kcal/mol,
generating methanol precursors methyl bisulfate (CH<sub>3</sub>OSO<sub>3</sub>H) and methanesulfonic acid (CH<sub>3</sub>SO<sub>3</sub>H)
via concurrent faradaic and nonfaradaic reaction pathways. This work
enables new electrochemical approaches for promoting rapid methane
monofunctionalization