Oxygen alkane oxidation

TS-1 is a material that perfectly fits the definition of single-site catalyst discussed in the previous Section. It is an active and selective catalyst in a number of low-temperature oxidation reactions with aqueous H2O2 as the oxidant. Such reactions include phenol hydroxylation [9,17], olefin epoxida-tion [9,10,14,17,40], alkane oxidation [11,17,20], oxidation of ammonia to hydroxylamine [14,17,18], cyclohexanone ammoximation [8,17,18,41], conversion of secondary amines to dialkylhydroxylamines [8,17], and conversion of secondary alcohols to ketones [9,17], (see Fig. 1). Few oxidation reactions with ozone and oxygen as oxidants have been investigated. 

It is important to emphasize that the atomic oxygen anion-radical plays a role in catalytic oxidation occnrring on varions oxide surfaces. For instance, O reacts with methane at room temperatnre over varions metal oxides (Lee and Gralowsky 1992). On solid catalysis, Q- is more reactive toward alkanes and alkenes than other ionic oxygen species. Iwamoto and Lnnsford (1980) assumed that O is the active oxygen species oxidizing benzene to phenol on with 70% selectivity at... 

This paper is a summary of our current understanding of this system. In particular, we will be discussing the observations in terms of selectivity with respect to the availability of reactive lattice oxygen. The organization of the paper is as follows. First, the general features of the reaction scheme for alkane oxidation on vanadate catalysts will be presented. This is followed by a discussion of results on the effect of ease of removal of oxygen from the lattice on the selectivity, and then a discussion on the importance of the atomic arrangement of the active sites. 

Other catalysts for alkane oxidative dehydrogenation have also been reported in the patent literature. For example, it was claimed that a Na and Li phosphomolybdate produced 17% butadiene and 5% butenes at 600°C with a 1 1 mixture of butane and oxygen (13). 

Pseudomonas oleovorans contains P. oleovorans monooxygenase (POM), which is a typical co-hydroxylase for hydroxylation of the terminal methyl of alkanes as well as epoxidation of terminal olefins. The co-hydroxylation system of P. oleovorans was reconstituted from purified components, POM, rubredoxin, and a flavoprotein reductase [122], In the presence of NADH and oxygen, it oxidizes a wide range of aliphatic methyl alkyl sulfides. Enantioselectivities are very much dependent of the length of the alkyl chain of Me-S(0)-R, as exemplified by the following results ... 

Figure 16 Intermediates involved in alkane oxidation by cytochrome P450. Catalytic cycles involving either O2 and electrons (from NADPH), or a single oxygen atom donor (AO) are shown. Model reactions often use single oxygen atom donors AO such as iodosylbenzene, amine A-oxides and organic or inorganic hydroperoxides or peroxy acids ...

In a base-free medium (dry MeCN), Fe Ch activates HOOH to form a reactive intermediate that oxygenates alkanes, alkenes, and thioethers, and dehydrogenates alcohols and aldehydes. Table 11 summarizes the conversion efficiencies and product distributions for a series of alkene substrates subjected to the Fe Cfi/HOOH/MeCN system. The extent of the Fe Cb-induced monooxygenations is enhanced by higher reaction temperatures and increased concentrations of the reactants (substrate, Fe Cls, and HOOH). For 1-hexene (representative of all of the alkenes), a substantial fraction of the product is the dimer of 1-hexene oxide, a disubstituted dioxane. With other organic substrates (RH), Fe Cb activates HOOH for their monooxygenation the reaction efficiencies and product distributions are summarized in Tables 11(b). In the case of alcohols, ethers, and cyclohexane, a snbstantial fraction of the product is the alkyl chloride, and with aldehydes, for example, PhCHO, the acid chloride represents one-half of the product. In the absence of snbstrate the Fe Cls/MeCN system catalyzes the rapid disproportionation of HOOH to O2 and H2O. 

For the singlet-oxygen photochemical reaction or for the complete reaction mixture when illumination conditions and O2 pressures cause the singlet-oxygen mediated reaction to dominate, alkane oxidation continues for more than 6 h as shown in Figure 2. 

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