Periodate-Mediated Aerobic Oxidation of Sulfides over a Bifunctional Porphyrin-polyoxometalate Catalyst: Photosensitized Singlet Oxygen Oxidation of Iodate to Periodate

Abstract

Regeneration of terminal oxidants by molecular oxygen in metal-catalyzed oxidations of organic substrates has the advantage of avoiding the use of stoichiometric amounts of hazardous and/or expensive reagents to meet (some of) the green chemistry requirements. In the present study, photosensitized singlet oxygen oxidation of iodate to periodate has been used to regenerate the oxidant in polyoxometalate (POM)-catalyzed oxidation of sulfides to sulfoxides with periodate in water. To the best of our knowledge, it is the first report on singlet oxygen oxidation of iodate to periodate. In order to determine the contribution of photooxidation and oxidation pathways in the formation of sulfoxide, the oxidation of diphenyl sulfide with a very low reactivity toward aerobic photooxidation was studied; a sevenfold increase in the conversion of the sulfide to the diphenyl sulfoxide was observed for the reaction conducted in the presence of H2TMPyP-PW12O40/IO3 –/O2/hν compared to that in the presence of H2TMPyP-PW12O40/O2/hν. Also, under the same conditions, a ca. 1.5-fold increase was observed in the case of methyl phenyl sulfide, which shows high reactivity toward both the oxidation and photooxidation reactions. A porphyrin-POM nanocomposite formed by the electrostatic immobilization of meso-tetra­(N-methylpyridinium-4-yl)­porphyrin (H2TMPyP) on PW12O40 was employed for the one-pot oxidation and photooxidation reactions. Field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), diffuse-reflectance UV–vis spectroscopy, thermal gravimetric analysis, and Fourier transform infrared were used to characterize the formation of the hybrid compound. An average particle size of 42 nm was estimated for H2TMPyP-PW12O40 from XRD peak broadening using the Scherrer equation. Also, FESEM images showed the formation of nearly spherical nanoparticles with a size of ca. 200 nm. The redshift of the Soret band of H2TMPyP upon immobilization on POM was attributed to strong N–H···O hydrogen-bond interactions between POM and porphyrin.

Exploring Electron Transfer Mechanism in Synergistic Interactional Reduced Polyoxometalate-Based Cu(I)–Organic Framework for Photocatalytic Removal of U(VI)

“…Polyoxometalates (POMs) are a class of metal-oxide cluster compounds and mostly consist of early transition metals (TM) polyhedral (MO x ) (TM = Ta, V, W, Nb, and Mo) in their highest oxidation state. − POMs possess similar architecture components and electronic characteristics to conventional metal oxide semiconductors such as TiO 2 , which both contain oxygen atoms and transition metal atoms with d 0 electron configuration . Therefore, POMs exhibit semiconductor-like properties and have been widely investigated in photocatalytic field. − One significant characteristic for POMs is “electron-sponge” property, which ensures they can maintain structural integrity when they gain or lose electrons. , This advantage makes polyoxometalate-based metal–organic frameworks (POMOFs) ideal models to study the electron transfer pathways.…”