Olefin epoxidation with hydrogen peroxide catalyzed by lacunary polyoxometalate [γ-SiW10O34(H2O)2]4-

ne tetra-n-butylammonium (TBA) salt of the divacant Keggin-type polyoxometalate [TBA](4)[gamma-SiW10O34-(H2O)(2)] (1) catalyzes the oxygen-transfer reactions of olefins, allylic alcohols, and sulfides with 30% aqueous hydrogen peroxide. The negative Hammett rho(+) (-0.99) for the competitive oxidation of p-substituted styrenes and the low value of (nucleophilic oxidation)/(total oxidation), X-SO = 0.04, for I-catalyzed oxidation of thianthrene 5-oxide (SSO) reveals that a strongly electrophilic oxidant species is formed on I. The preferential formation of trans-epoxide during epoxidation of 3-methyl-1-cyclohexene demonstrates the steric constraints of the active site of I. The I-catalyzed epoxidation proceeds with an induction period that disappears upon treatment of I with hydrogen peroxide. Si-29 and W-183 NMR spectroscopy and CSI mass spectrometry show that reaction of I with excess hydrogen peroxide leads to fast formation of a diperoxo species, [TBA](4)[gamma-SiW10O32(O-2)(2)] (11), with retention of a gamma-Keggin type structure. Whereas the isolated compound 11 is inactive for stoichiometric epoxidation of cyclooctene, epoxidation with 11 does proceed in the presence of hydrogen peroxide. The reaction of 11 with hydrogen peroxide would form a reactive species (111), and this step corresponds to the induction period observed in the catalytic epoxidation. The steric and electronic characters of III are the same as those for the catalytic epoxidation by I. Kinetic, spectroscopic, and mechanistic investigations show that the present epoxidation proceeds via III.