Dodecatungsto-silicic H(4)SiW(12)O(40) and -phosphoric acids H(3)PW(12)O(40) were deposited on silica by a classical impregnation technique. The resulting materials were studied by in situ Raman and infrared spectroscopy, XPS and by solid-state (1)H MAS NMR as a function of their dehydroxylation temperature. The data show that in the case of H(3)PW(12)O(40) three silanol groups are protonated while in the case of H(4)SiW(12)O(40) at least one acidic proton remains. Upon heating this proton reacts leading to a disordered structure and a broadening of the W-O Raman bands.

The H 3 PW 12 O 40 and H 4 SiW 12 O 40 heteropolyacids supported on silica were studied by 1 H MAS NMR as a function of both the coverage and the dehydroxylation temperature. The signal at ca. 8 ppm attributed to the highly acidic protons of the anhydrous form of the heteropolyacid was never observed in the case of the phosphotungstic polyanion supported on silica while it was clearly present in the case of the silicotungstic species. These results explain the different activities of the two supported heteropolyacids in acid reactions involving strong acid sites. To cite this article: A.

Silica-supported Keggin-type heteropolyacids react with platinum(II) complexes displaying a Pt-CH3 group, leading to the evolution of methane and the formation of an organometallic fragment grafted on the polyacid. This species has been characterized by various physicochemical methods such as microanalyses, infrared spectroscopy, solid-state 1D and 2D MAS NMR, and EXAFS. Molecular models were also prepared by reaction of the nonsupported anhydrous polyacid with the platinum(II) methyl complexes. These compounds were characterized in solution by multinuclear NMR (1H, 13C, 183W, and 195Pt) and in the solid state by X-ray diffraction on monocrystals. All data indicate that the interaction between the platinum complex and the polyoxometalate is weak and that this system is better expressed as an organometallic platinum salt of the supported heteropolyacid. This complex can be seen as one of the intermediates in the partial oxidation of methane to methanol, its synthesis being the reverse reaction of the methane activation.