Activation mechanism of hydrogen peroxide by a divanadium-substituted polyoxometalate [γ-PV₂W₁₀O₃₈(μ-OH)₂]^3-: A...

In the present paper, the reaction mechanism corresponding to activation of hydrogen peroxide (H₂O₂) by a divanadium-substituted polyoxometalate (POM) [γ-PV₂W₁₀O₃₈(μ-OH)₂]^3- (I) to form catalytic active species, peroxo complex [γ-PV₂W₁₀O₃₈(μ-η²,η²-O₂)]^3- (III), was studied by using the density functional theory (DFT) calculations method with B3LYP functional. The results indicate that coordination of H₂O₂ to I proceeds via a vanadium-center-assisted proton transfer pathway to remove the first water molecule and form a hydroperoxy intermediate [γ-PV₂W₁₀O₃₈(μ-OH) (μ-OOH)]^3- (II). And intermediate II occurs through three successive water-assisted proton transfer steps to remove the second water molecule and finally forms catalytic active species. The calculated overall energy profiles show that coordination of H₂O₂ to vanadium center requires a proton transfer barrier of about 24 kcal mol^-1. A detailed comparison of molecular geometries and electronic structure shows that the catalytic active species has a very interesting structural feature, where a superoxide radical (O₂^-) was embedded into two vanadium centers, and may be a potential nucleophile. The unique withdrawing electron properties and flexible bonding ability of the γ-Keggin-type POM ligand contribute to the formation of O₂^- radical. The tunable alternate arrangement of W-O bond series in γ-Keggin-type POM ligand contributes to the flexibility of the γ-Keggin-type POM ligand. Meanwhile, our DFT calculations show a good performance of B3LYP-gauge-independent atomic orbital (IGAIM) method for the calculation of ¹H NMR parameters of divanadium-substituted phosphotungstate.