Consequences of substituting framework metals in polyoxometalates on H-atom uptake: proton-coupled electron transfer at a Keggin-type polyoxomolybdate

Abstract

The proton-coupled electron transfer to the surface of a Keggin-type polyoxomolybdate, [ⁿBu₄N]₃[PMo₁₂O₄₀], is described. The thermochemistry of surface O–H bonds generated upon reduction/protonation of the assembly is determined (∼67 kcal mol⁻¹). Kinetic investigations provide evidence that proton–electron pairs are added to the polyoxomolybdate surface through a concerted mechanism.