Oxidation reactions, transition-metal vanadium

The carbides and nitrides of the early transition metals, vanadium, niobium, and molybdenum, are known to possess good catalytic properties. The compounds are synthesized by a temperature programmed reaction (TPR) method where a reactive gas is reacted with a precursor oxide as the temperature is uniformly increased. Results under similar reaction conditions are presented to compare the progress of the reaction, the formation of intermediate phases, and the development of surface areas. The increase in surface area is influenced by the phenomena of pseudomorphism and topotaxy. It is believed that pseudomorphism, found in all of the above syntheses, is associated with the development of internal pores, while topotaxy, found in some of the nitrides, maximizes this process to yield hi surface area products. 

Organic hydroperoxides have also been used for the oxidation of sulphoxides to sulphones. The reaction in neutral solution occurs at a reasonable rate in the presence of transition metal ion catalysts such as vanadium, molybdenum and titanium - , but does not occur in aqueous media . The usual reaction conditions involve dissolution of the sulphoxide in alcohols, ethers or benzene followed by dropwise addition of the hydroperoxide at temperatures of 50-80 °C. By this method dimethyl sulphoxide and methyl phenyl sulphoxide have been oxidized to the corresponding sulphone in greater than 90% yields . A similar method for the oxidation of sulphoxides has been patented . Unsaturated sulphoxides are oxidized to the sulphone without affecting the carbon-carbon double bonds. A further patent has also been obtained for the reaction of dimethyl sulphoxide with an organic hydroperoxide as shown in equation (19). 

One-electron reduction or oxidation of organic compounds provides a useful method for the generation of anion radicals or cation radicals, respectively. These methods are used as key processes in radical reactions. Redox properties of transition metals can be utilized for the efficient one-electron reduction or oxidation (Scheme 1). In particular, the redox function of early transition metals including titanium, vanadium, and manganese has been of synthetic potential from this point of view [1-8]. The synthetic limitation exists in the use of a stoichiometric or excess amount of metallic reductants or oxidants to complete the reaction. Generally, the construction of a catalytic redox cycle for one-electron reduction is difficult to achieve. A catalytic system should be constructed to avoid the use of such amounts of expensive and/or toxic metallic reagents. 

Other transition-metal oxidants can convert alkenes to epoxides. The most useful procedures involve /-butyl hydroperoxide as the stoichiometric oxidant in combination with vanadium, molybdenum, or titanium compounds. The most reliable substrates for oxidation are allylic alcohols. The hydroxyl group of the alcohol plays both an activating and a stereodirecting role in these reactions. /-Butyl hydroperoxide and a catalytic amount of VO(acac)2 convert allylic alcohols to the corresponding epoxides in good yields.44 The reaction proceeds through a complex in which the allylic alcohol is coordinated to... 

Vanadium oxide dispersed on supporting oxides (Si02 Al Oo, Ti02, etc.) are frequently employed as catalysts in reactions like partial oxidation and ammoxidation of hydrocarbons, and NO reduction. The modifications induced on the reactive properties of transition metal oxides like V20 when they are supported on an oxide carrier has been the subject matter of recent study. There is much evidence showing that the properties of a thin layer of a transition metal oxide interacting with the support are strongly modified as compared to the properties of the bulk oxide (1-3). In the recent past, increasing attention has been focussed... 

We studied the oxidation of cyclohexene at 70°C in the presence of cyclopentadienylcarbonyl complexes of several transition metals. As with the acetylacetonates, the metal center was the determining factor in the product distribution. The decomposition of cyclohexenyl hydroperoxide by the metal complexes in cyclohexene gave insight into the nature of the reaction. With iron and molybdenum complexes the product profile from hydroperoxide decomposition paralleled that observed in olefin oxidation. When vanadium complexes were used, this was not the case. Variance in product distribution between the cyclopentadienylcarbonyl metal-promoted oxidations as a function of the metal center were more pronounced than with the acetylacetonates. Results are summarized in Table V. 

In this paper we review the results of our systematic work on the catalytic and adsorptive properties of transition metal carbides (titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and iron). We focus our attention on the oxidation of hydrogen, carbon monoxide, ammonia, and the oxidative coupling of methane. The first two reactions are examples of complete (non-selective) oxidation, while the oxidation of ammonia simulates a selective oxidation process. The reaction of oxidative coupling of methane is being intensively explored at present as a means to produce higher hydrocarbons.5 10... 

The possibility of hydrogen activation on the surface of transition metal carbides has been supported by experiments in which WC was used as a promoter for the hydrogen oxidation reaction over the oxide catalyst V205.1 WC additions to V2O5 were shown to critically accelerate the reaction of H2 + 02 (so that under the same conditions the activities of V205 and WC were separately much lower). Moreover, WC additions to V205 boosted the reduction of vanadium oxide by hydrogen. Qualitatively,... 

Heteropoly catalysts have significant activities for the oxidation of isobutane into methacrolein and methacrylic acid. The yield increased up to 6% by vanadium substitution or salt formation, as follows. With Cs2.5Ni0.08H0.34+JrPV,Mo12 - O40, the highest conversion and selectivity were observed at x 1 (355). Increases in the reaction temperature to 613 K led to increased yields, up to 9.0%. A similar increase in the yield resulted from the substitution of As for P as a heteroatom or from the addition of various transition metals (106, 356). 

This article is focused on HDN, the removal of nitrogen from compounds in oil fractions. Hydrodemetallization, the removal of nickel and vanadium, is not discussed, and HDS is discussed only as it is relevant to HDN. Section II is a discussion of HDN on sulfidic catalysts the emphasis is on the mechanisms of HDN and how nitrogen can be removed from specific molecules with the aid of sulfidic catalysts. Before the discussion of these mechanisms, Section II.A provides a brief description of the synthesis of the catalyst from the oxidic to the sulfidic form, followed by current ideas about the structure of the final, sulfidic catalyst and the catalytic sites. All this information is presented with the aim of improving our understanding of the catalytic mechanisms. Section II.B includes a discussion of HDN mechanisms on sulfidic catalysts to explain the reactions that take place in today s industrial HDN processes. Section II.C is a review of the role of phosphate and fluorine additives and current thinking about how they improve catalytic activity. Section II.D presents other possibilities for increasing the activity of the catalyst, such as by means of other transition-metal sulfides and the use of supports other than alumina. 

Hie first of Sharpless s reactions is an oxidation of alkenes by asymmetric epoxidation. You met vanadium as a transition-metal catalyst for epoxidation with r-butyl hydroperoxide in Chapter 33, and this new reaction makes use of titanium, as titanium tetraisopropoxide, Ti(OiPr)4, to do the same thing. Sharpless surmised that, by adding a chiral ligand to the titanium catalyst, he might be able to make the reaction asymmetric. The ligand that works best is diethyl tartrate, and the reaction shown below is just one of many that demonstrate that this is a remarkably good reaction. 

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