Surface ligand length influences kinetics of H-atom uptake in polyoxovanadate-alkoxide clusters

The uptake of hydrogen atoms (H-atoms) at reducible metal oxide nanocrystal surfaces has implications in catalysis and energy storage. However, it is often difficult to gain insight into the physicochemical factors that dictate the thermodynamics and kinetics of H-atom transfer to the surface of these assemblies. Recently, our research group has demonstrated the formation of oxygen-atom (O-atom) defects in polyoxovanadate-alkoxide (POV-alkoxide) clusters via conversion of surface oxido moieties to aquo ligands, which can be accomplished via addition of two H-atom equivalents. Here, we present the dependence of O-atom defect formation via H-atom transfer at the surface of vanadium oxide clusters on the length of surface alkoxide ligands. Analysis of H-atom transfer reactions to low-valent POV-alkoxide clusters [V₆O₇(OR)₁₂]^1- (R = Me, Et, Pr, Bu) reveals that the length of primary alkoxide surface ligands does not significantly influence the thermodynamics of these processes. However, surface ligand length has a significant impact on the kinetics of these PCET reactions. Indeed, the methoxide-bridged cluster, [V₆O₇(OMe)₁₂]^1- reacts ∼20 times faster than the other derivatives evaluated. Interestingly, as the aliphatic linkages are increased in size from -C₂H₅ to -C₄H₉, reaction rates remain consistent, suggesting restricted access to available ligand conformers as a result of the incompatibility of the aliphatic ligands and acetonitrile may buffer further changes to the rate of reaction.