The development of visible-light-induced photocatalysts for chemoselective functional group transformations has received considerable attention. Polyoxometalates (POMs) are potential materials for efficient photocatalysts because their properties can be precisely tuned by changing their constituent elements and structures and by the introduction of additional metal cations. Furthermore, they are thermally and oxidatively more stable than the frequently utilized organometallic complexes. The visible-light-responsive tetranuclear cerium(III)-containing silicotungstate TBA6[{Ce(H2O)}2{Ce(CH3CN)}2(μ4-O)(γ-SiW10O36)2] (CePOM; TBA=tetra-n-butylammonium) has now been synthesized; when CePOM was irradiated with visible light (λ>400 nm), a unique intramolecular Ce(III)-to-POM(W(VI)) charge transfer was observed. With CePOM, the photocatalytic oxidative dehydrogenation of primary and secondary amines as well as the α-cyanation of tertiary amines smoothly proceeded in the presence of O2 (1 atm) as the sole oxidant.

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A novel dialuminum-substituted silicotungstate TBA(3)H[gamma-SiW(10)O(36){Al(OH(2))}(2)(mu-OH)(2)] x 4 H(2)O (1, TBA = tetra-n-butylammonium) was synthesized by the reaction of the potassium salt of [gamma-SiW(10)O(36)](8-) (SiW10) with 2 equiv of Al(NO(3))(3) in an acidic aqueous medium. It was confirmed by the X-ray crystallographic analysis that compound 1 was a monomer of the gamma-Keggin dialuminum-substituted silicotungstate with the {Al(2)(mu-OH)(2)} diamond core. The cluster framework of 1 maintained the gamma-Keggin structure in the solution states. The reaction of 1 with pyridine yielded TBA(3)[(C(5)H(5)N)H][gamma-SiW(10)O(36){Al(C(5)H(5)N)}(2)(mu-OH)(2)] x 2 H(2)O (2), and the molecular structure was successfully determined by the X-ray crystallographic analysis. In compound 2, two of three pyridine molecules coordinated to the axial positions of aluminum centers and one of them existed as a pyridinium cation, showing that compound 1 has two Lewis acid sites and one Brønsted acid site. Compound 1 showed high catalytic activity for the intramolecular cyclization of citronellal derivatives such as (+)-citronellal (3) and 3-methylcitronellal (4) without formation of byproduct resulting from etherification and dehydration. For the 1-catalyzed cyclization of 3, the diastereoselectivity toward (-)-isopulegol (3a) reached ca. 90% and the value was the highest level among those with reported systems so far. The reaction rate for the 1-catalyzed cyclization of 3 decreased by the addition of pyridine, and the cyclization hardly proceeded in the presence of 2 equiv of pyridine with respect to 1. On the other hand, the reaction rate and diastereoselectivity to 3a in the presence of 2,6-lutidine were almost the same as those in the absence. Therefore, the present cyclization is mainly promoted by the Lewis acid sites (aluminum centers) in 1. DFT calculations showed that the formation of the transition state to produce 3a is sterically and electronically more favorable than the other three transition states for the present 1-catalyzed cyclization of 3.

An Ag4 diamond is encapsulated by silicotungstate ligands in TBA8[Ag4(DMSO)2(γ‐H2SiW10O36)2]⋅2 DMSO⋅2 H2O (Ag4; DMSO=dimethyl sulfoxide, TBA=tetra‐n‐butylammonium), which was obtained by reaction of TBA4H4[γ‐SiW10O36] with AgOAc in an organic medium. Polyoxometalate Ag4 (see picture) selectively catalyzes hydrolytic oxidation of various silanes to the corresponding silanols in high yields (72–96 %).

By the reaction of TBA(4)H(4)[γ-SiW(10)O(36)] (TBA = tetra-n-butylammonium) with AgOAc (OAc = acetate) using dimethylphenylsilane as a reductant in acetone, a unique polyoxometalate containing a discrete octahedrally shaped [Ag(6)](4+) cluster, TBA(8)[Ag(6)(γ-H(2)SiW(10)O(36))(2)]·5H(2)O, could be synthesized, and the molecular structure was determined.