Ag -Mediated Electrocatalytic Ambient CH Functionalization Inspired by HSAB Theory.

Although most class (b) transition metals have been studied in regard to CH activation, divalent silver (Ag ), possibly owing to its reactive nature, is the only class (b) high-valent transition metal center that is not yet reported to exhibit reactivities towards CH activation. We now report that electrochemically generated Ag metalloradical readily functionalizes CH into methyl bisulfate (CH OSO H) at ambient conditions in 98 % H SO . Mechanistic investigation experimentally unveils a low activation energy of 13.1 kcal mol , a high pseudo-first-order rate constant of CH activation up to 2.8×10  h at room temperature and a CH pressure of 85 psi, and two competing reaction pathways preferable towards CH activation over solvent oxidation. Reaction kinetic data suggest a Faradaic efficiency exceeding 99 % beyond 180 psi CH at room temperature for potential chemical production from widely distributed natural gas resources with minimal infrastructure reliance.