O 2 reduction via proton-coupled electron transfer by a V(III) aquo on a polyoxovanadate-alkoxide cluster.

We report the transfer of H-atoms from a reduced polyoxovanadate alkoxide [ n Oct 4 N][V 6 O 6 (OH 2 )(OMe) 12 ] via concerted proton-electron transfer. Oxygen reduction is compared between bridging and terminal O-H bonds revealing similar mechanisms, providing new insight to design criteria for metal-oxide electrocatalysts that faciliate oxygen reduction by concerted-proton electron transfer.