Oxidation reactions using other metal oxidants

The fundamental mechanism of the dihydroxylation of olefins remained unclear for a long time. Two different mechanisms, concerted [3+2] and stepwise [2+2] were popular, plausible, mechanisms for the reaction [84, 85]. The controversy about the reaction mechanism was finally resolved after the thorough work of several experimental [84, 85] and theoretical [86] research groups. A scientific consensus emerged considering the [3+2] mechanism as the operative one [87]. Nevertheless, in very special cases and using other metal oxides, the activation barrier for the stepwise mechanism is lower in energy than for the concerted one [88, 89]. Other mechanisms, such as a diradical mechanism, have been also discussed [90]. 

The oxidations of thiols to disulphides by manganese(m) trisacetyl-acetonate are relatively slow compared to their rates of reaction by other metal ions. The use of manganese(m) acetate in oxidations using free radicals has been reported. When a solution of oct-l-ene, acetone, and manganese(m) acetate in acetic acid is heated, three major products are reported, the initial step involving the oxidation of acetone... 

The potential of the reaction is given as = (cathodic — anodic reaction) = 0.337 — (—0.440) = +0.777 V. The positive value of the standard cell potential indicates that the reaction is spontaneous as written (see Electrochemical processing). In other words, at thermodynamic equihbrium the concentration of copper ion in the solution is very small. The standard cell potentials are, of course, only guides to be used in practice, as rarely are conditions sufftciendy controlled to be called standard. Other factors may alter the driving force of the reaction, eg, cementation using aluminum metal is usually quite anomalous. Aluminum tends to form a relatively inert oxide coating that can reduce actual cell potential. 

A number of metal chelates containing transition metals in their higher oxidation states are known to decompose by one electron transfer process to generate free radical species, which may initiate graft copolymerization reactions. Different transition metals, such as Zn, Fe, V, Co, Cr, Al, etc., have been used in the preparation of metal acetyl acetonates and other diketonates. Several studies demonstrated earlier that metal acetyl acetonates can be used as initiators for vinyl polymeriza-... 

The observation that addition of imidazoles and carboxylic acids significantly improved the epoxidation reaction resulted in the development of Mn-porphyrin complexes containing these groups covalently linked to the porphyrin platform as attached pendant arms (11) [63]. When these catalysts were employed in the epoxidation of simple olefins with hydrogen peroxide, enhanced oxidation rates were obtained in combination with perfect product selectivity (Table 6.6, Entry 3). In contrast with epoxidations catalyzed by other metals, the Mn-porphyrin system yields products with scrambled stereochemistry the epoxidation of cis-stilbene with Mn(TPP)Cl (TPP = tetraphenylporphyrin) and iodosylbenzene, for example, generated cis- and trans-stilbene oxide in a ratio of 35 65. The low stereospecificity was improved by use of heterocyclic additives such as pyridines or imidazoles. The epoxidation system, with hydrogen peroxide as terminal oxidant, was reported to be stereospecific for ris-olefins, whereas trans-olefins are poor substrates with these catalysts. 

Various a-addition reactions are observed to be metal- or acid-catalyzed, or to be uncatalyzed. In this review only the metal-catalyzed reactions will be discussed, since it is generally assumed that metal isocyanide complexes are involved in these systems. A number of metal-catalyzed a-addition reactions have been mentioned recently. Copper(I) oxide seems to be the most commonly used catalyst, although other metal complexes sometimes are satisfactory. Table III presents a partial survey of this work. 

Tin finds widespread use because of its resistance to corrosion, or as foil or to provide protective coats/plates for other metals. Properties of lead which make industrial application attractive surround its soft, plastic nature permitting it to be rolled into sheets or extruded through dies. In the finely-divided state lead powder is pyrophoric in bulk form the rapidly-formed protective oxide layer inhibits further reaction. It dissolves slowly in mineral acids. Industrial uses include roofing material, piping, and vessel linings, e.g. for acid storage. 

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