Hydrogen peroxide titanium peroxo complex

The workers proposed that alkyl hydroperoxides and aqueous hydrogen peroxide interact with TS-1 in a similar manner, forming titanium alkyl peroxo complexes and titanium peroxo complexes, respectively. However, the titanium alkyl peroxo complexes were not active because the substrate could not enter the void due to steric effects. Consequently, no activity was possible for either alkane hydroxylation or alkene epoxidation. Comparison with Ti02-Si02/alkyl hydroperoxide for alkane and alkene oxidation indicated that this material was active because the oxidation took place on the surface and not in the pores. Figures 4.4 and 4.5 show the possible mechanisms in operation for the oxidation of alkenes and alkanes with a TS-1/hydrogen peroxide system. 

The work of Davis was, however, unable to distinguish which oxygen was attacked on the titanium peroxo complex when the alkene co-ordinates. Therefore, Neurock and Manzer conducted a theoretical study of the mechanism of alkene epoxidation using TS-1 with aqueous hydrogen peroxide.32 The workers concluded that their calculations to predict both the structure and relative bands in the IR spectra for TS-1 were in good agreement with experimental data. The calculations indicated that the oxygen closest to the titanium centre was the active site for alkene attack. The result was the direct formation of... 

Aqueous solutions containing titanium(IV) give an orange-yellow colour on addition of hydrogen peroxide the colour is due to the formation of peroxo-titanium complexes, but the exact nature of these is not known. 

The colour sequence already described, for the reduction of van-adium(V) to vanadium(II) by zinc and acid, gives a very characteristic test for vanadium. Addition of a few drops of hydrogen peroxide to a vanadate V) gives a red colour (formation of a peroxo-complex) (cf. titanium, which gives an orange-yellow colour). 

Peroxidic Compounds. When hydrogen peroxide is added to a solution of titanium(IV) compounds, an intense, stable, yellow solution is obtained, which forms the basis of a sensitive method for determining small amounts of titanium. The color probably results from the peroxo complex [Ti(02)(0H)(H20)J, and crystalline salts such as K2[Ti(02)(S0 2] H20 can be isolated from alkaline solutions. The peroxo ligand is bidentate the two oxygen atoms ate equidistant from the titanium (98). 

A titanium complex (1) with a salen ligand is an efficient catalyst for the enan-tioselective epoxidation of alkenes with hydrogen peroxide as the terminal oxidant. The participation of a titanium-peroxo species, activated by hydrogen bonding, in the reaction, has been postulated.73... 

Many hydroxylated linalools [including compounds 105, 106, 108, and 110, both (Z)- and ( )-isomers], as well as the epoxides of both furanoid (109) and pyranoid (see section on pyrans) linalyl oxides, have been identified in papaya fruit (Carica papaya). At the same time, the first reported occurrence of die two linalool epoxides (112) in nature was made. These epoxides are well known to be unstable and easily cyclized (see Vol. 2, p. 165) and have been made by careful peracid oxidation of linalool. An interesting new method has now been described. While the vanadium- or titanium-catalyzed epoxidation of geraniol (25) gave the 2,3-epoxide (see above), as does molybdenum-catalyzed epoxidation with hydrogen peroxide, the epoxidation of linalool (28) with molybdenum or tungsten peroxo complexes and hydrogen peroxide led, by reaction on the 6,7-double bond, to 112. ... 

This method is more complicated than the mixed alkoxide technique (Fig. 1). Hydrogen peroxide is added to the titanium-containing solution in order to form stable peroxo-complexes able to release slowly the metal ion during the hydrothermal treatment. The gel composition, the hydrothermal conditions and the characteristics of the products are similar to those described for the mixed alkoxide method. 

Solid catalysts may also be used for reactions implying oxidants differ by dioxygen. The most popular case is that of titanium-silicalite catalysts for oxidation with hydrogen peroxide. The active species in the presence of water has been characterised to be a side-on peroxo complex characterised by a Raman-detected 0-0 stretching at 618 cm Upon drying, this species converts into a hydroperoxo species characterised using IR by an 0-0 stretching at 837 cm and a broad OH band at 3400 cm ... 

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