This work is devoted to the study of the active species present on the TS-1-H 2 O 2 /H 2 O catalytic system and to the elucidation of the mechanisms of formation and interconversion of these species. In particular new experimental data and computational evidence are reported concerning (i) the acidic character of hydroperoxo species, (ii) the role of water in the hydroperoxo-peroxo interconversion, and (iii) the role of water as coreactant in favoring the H 2 O 2 adsorption at Ti sites. It is demonstrated that gentle drying of the TS-1-H 2 O 2 / H 2 O system leads to the transformation of the yellow peroxo groups into noncolored species, still located at Ti centers. The process is reversible and the colored species can be partially restored again by successive rehydration. As the hydroperoxo and peroxo species have different oxidizing ability, these results indicate that the presence of water molecules at hydrophilic Ti sites can correlate with the catalytic activity. As it is well-known, hydroperoxo and peroxo species are unstable and their concentration declines with aging. However, UV-vis spectroscopic results demonstrate that small fractions of peroxo species (characterized by a cream color) persist on the sample even after prolonged aging. On this basis and on EXAFS results, a comprehensive scheme of the formation and mutual conversion of oxidized species is concluded. Spectroscopic results, supported by acidity measurements and titration of active oxygen content, show the following: (i) the O-O species, responsible to the yellow color of the catalyst, is a side-on peroxo complex, probably generated by the reversible rupture of one Ti-O-Si bridge, with the formation of Ti(O 2 H) and H-O-Si groups; (ii) the stability of this peroxo complex is low in the absence of an excess of H 2 O; (iii) a strong enhancement of the acidity of the TS-1/H 2 O 2 /H 2 O system with respect to that of TS-1/H 2 O has been observed, demonstrating a synergic role between Ti(IV) centers and hydrogen peroxide; and (iv) a small fraction of oxidized species has a negligible oxidizing ability and probably does not play any role in the catalysis.

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The oxidative cleavage of alkenes to carboxylic acids with 40% w/v aqueous hydrogen peroxide catalyzed by methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate(3-) (Ia) is reported to occur in high yields and selectivities under two-phase conditions in the absence of organic solvents. On the basis of a study of the reaction, two main reaction pathways leading to acids have been recognized, the first one involving the perhydrolysis and the second one the hydrolysis of the epoxide initially formed. The "perhydrolytic" reaction pathway appears to play a primary role in the oxidation of medium- and long-chain alkenes to acids, while it intervenes to a rather limited extent in the oxidation of arylalkenes and C(5)-C(7) cycloalkenes. The occurrence of this pathway has been proved by the isolation of the intermediate beta-hydroperoxy alcohols and their transformation into acids with H(2)O(2) and Ia. The course of this transformation, involving an initial oxidation (to alpha-oxo hydroperoxide) or decomposition (to carbonyl compounds) of the beta-hydroperoxy alcohol intermediate, is described. The primary oxidation products, alpha-hydroperoxy ketones, have been isolated in the case of internal beta-hydroperoxy alcohols, whereas their presence has been evidenced with terminal beta-hydroperoxy alcohols bearing a secondary hydroxy group. Hydrogen peroxide concentration appears to exert a remarkable influence on medium acidity, and its effects on the reaction efficiency are shown.

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