Rapid Electrochemical Methane Functionalization Involves Pd-Pd Bonded Intermediates.

High-valent Pd complexes are potent agents for the oxidative functionalization of inert C-H bonds, and it was previously shown that rapid electrocatalytic methane monofunctionalization could be achieved by electro-oxidation of Pd to a critical dinuclear Pd intermediate in concentrated or fuming sulfuric acid. However, the structure of this highly reactive, unisolable intermediate, as well as the structural basis for its mechanism of electrochemical formation, remained elusive. Herein, we use X-ray absorption and Raman spectroscopies to assemble a structural model of the potent methane-activating intermediate as a Pd dimer with a Pd-Pd bond and a 5-fold O atom coordination by HSO ligands at each Pd center. We further use EPR spectroscopy to identify a mixed-valent M-M bonded Pd species as a key intermediate during the Pd-to-Pd oxidation. Combining EPR and electrochemical data, we quantify the free energy of Pd dimerization as <-4.5 kcal/mol for Pd and <-9.1 kcal/mol for Pd. The structural and thermochemical data suggest that the aggregate effect of metal-metal and axial metal-ligand bond formation drives the critical Pd dimerization reaction in between electrochemical oxidation steps. This work establishes a structural basis for the facile electrochemical oxidation of Pd to a M-M bonded Pd dimer and provides a foundation for understanding its rapid methane functionalization reactivity.