Transition-Metal Ions and Hydroperoxides

Rate Constants of the Reaction of Transition Metal Ions and Complexes with Hydroperoxides... 

In the presence of traces of transition-metal ions, lipid hydroperoxides are a continuous source for the formation of new alkoxy and peroxy radicals which initiate new chain reactions and therefore act as amplifiers for the initial free radical event. 

However, hydroperoxide decomposers may act by much more complicated mechanisms. Many sulfur compounds, like the thiodipropionate esters (DRTPs) or the metal dialkyldithiocarbamates (MRDCs) are oxidised to sulfur acids (sulfinic, sulfonic and SO3) which are ionic catalysts for the non-radical decomposition of hydroperoxides. The MRDCs are particularly important since, unlike the phosphites, they also contain complex transition metal ions and when M is a transition metal ion e.g. Ni) they are also UVAs. 

The free radical chain reactions (3), (4), initiated by hydroperoxides in the presence of transition metal ions and oxygen (5)-(8), continues in hydrocarbon polymers so long as oxygen is present in the system with the accumulation of abiotically stable carboxylic acids. However, in microbially active environments, carboxylic acids are bioassimilated by micoorganisms so that the carboxylic acids are in dynamic equilibrium in the system. It has been demonstrated experimentally [21,22] that pure strains of bacteria (in... 

Eithei oxidation state of a transition metal (Fe, Mn, V, Cu, Co, etc) can activate decomposition of the hydiopeioxide. Thus a small amount of tiansition-metal ion can decompose a laige amount of hydiopeioxide. Trace transition-metal contamination of hydroperoxides is known to cause violent decompositions. Because of this fact, transition-metal promoters should never be premixed with the hydroperoxide. Trace contamination of hydroperoxides (and ketone peroxides) with transition metals or their salts must be avoided. 

This reaction is one example of several possible radical transition-metal ion interactions. The significance of this and similar reactions is that radicals are destroyed and are no longer available for initiation of useful radical reactions. Consequentiy, the optimum use levels of transition metals are very low. Although the hydroperoxide decomposes quickly when excess transition metal is employed, the efficiency of radical generation is poor. 

With most transition metals, eg, Cu, Co, and Mn, both valence states react with hydroperoxides via one electron transfer (eqs. 11 andl2). Thus, a small amount of transition-metal ion can decompose a large amount of hydroperoxide and, consequendy, inadvertent contamination of hydroperoxides with traces of transition-metal impurities should be avoided. 

The reactions of alkyl hydroperoxides with ferrous ion (eq. 11) generate alkoxy radicals. These free-radical initiator systems are used industrially for the emulsion polymerization and copolymerization of vinyl monomers, eg, butadiene—styrene. The use of hydroperoxides in the presence of transition-metal ions to synthesize a large variety of products has been reviewed (48,51). 

Alkyl hydroperoxides are among the most thermally stable organic peroxides. However, hydroperoxides are sensitive to chain decomposition reactions initiated by radicals and/or transition-metal ions. Such decompositions, if not controlled, can be auto accelerating and sometimes can lead to violent decompositions when neat hydroperoxides or concentrated solutions of hydroperoxides are involved. 

The radicals are destroyed and are not available to take part in the desired radical reactions, eg, polymerizations. Thus, transition-metal ion concentrations of metal—hydroperoxide initiating systems are optimized to maximize radical generation. 

Metal-Catalyzed Oxidation. Trace quantities of transition metal ions catalyze the decomposition of hydroperoxides to radical species and greatiy accelerate the rate of oxidation. Most effective are those metal ions that undergo one-electron transfer reactions, eg, copper, iron, cobalt, and manganese ions (9). The metal catalyst is an active hydroperoxide decomposer in both its higher and its lower oxidation states. In the overall reaction, two molecules of hydroperoxide decompose to peroxy and alkoxy radicals (eq. 5). 

Common components of many redox systems are a peroxide and a transition metal ion or complex. The redox reactions of peroxides are covered in the sections on those compounds. Discussion on specific redox systems can be found in sections on diacyl peroxides (3,3.2.1.5), hydroperoxides (3,3.2.5) persulfate (3.3.2.6.1) and hydrogen peroxide (3.3.2.6,2). 

Variable valence transition metal ions, such as Co VCo and Mn /Mn are able to catalyze hydrocarbon autoxidations by increasing the rate of chain initiation. Thus, redox reactions of the metal ions with alkyl hydroperoxides produce chain initiating alkoxy and alkylperoxy radicals (Fig. 6). Interestingly, aromatic percarboxylic acids, which are key intermediates in the oxidation of methylaromatics, were shown by Jones (ref. 10) to oxidize Mn and Co, to the corresponding p-oxodimer of Mn or Co , via a heterolytic mechanism (Fig. 6). 

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). 

Retard efficiently oxidation of polymers catalysed by metal impurities. Function by chelation. Effective metal deactivators are complexing agents which have the ability to co-ordinate the vacant orbitals of transition metal ions to their maximum co-ordination number and thus inhibit co-ordination of hydroperoxides to metal ions. Main use of stabilisation against metal-catalysed oxidation is in wire and cable applications where hydrocarbon materials are in contact with metallic compounds, e.g. copper. 

Increase the oxidation rate of polymers, e.g. metal ions which increase the hydroperoxide decomposition rate. Photodegradation and thermal degradation are enhanced by transition metal ion containing pro-oxidants, such as iron dithiocarbamate (as opposed to nickel dithiocarba-mate, which acts as a photo-antioxidant). 

In real systems (hydrocarbon-02-catalyst), various oxidation products, such as alcohols, aldehydes, ketones, bifunctional compounds, are formed in the course of oxidation. Many of them readily react with ion-oxidants in oxidative reactions. Therefore, radicals are generated via several routes in the developed oxidative process, and the ratio of rates of these processes changes with the development of the process [5], The products of hydrocarbon oxidation interact with the catalyst and change the ligand sphere around the transition metal ion. This phenomenon was studied for the decomposition of sec-decyl hydroperoxide to free radicals catalyzed by cupric stearate in the presence of alcohol, ketone, and carbon acid [70-74], The addition of all these compounds was found to lower the effective rate constant of catalytic hydroperoxide decomposition. The experimental data are in agreement with the following scheme of the parallel equilibrium reactions with the formation of Cu-hydroperoxide complexes with a lower activity. 

Metal-deactivating antioxidants. Transition metal compounds decompose hydroperoxides with the formation of free radicals, thereby increasing the rate of oxidation. Such an enhanced oxidation can be slowed down by the addition of a compound that interacts with metal ions to form complexes that are inactive with respect to hydroperoxides. Diamines, hydroxy acids, and other bifunctional compounds exemplify this type of antioxidants. 

A survey of crystal structures of 29 compounds (Table 8), in which the alkyl hydroperoxide anions serves as ligand to metal ions, transition metal ions or group 13-17 elements, provides a mean 0—0 bond length of 1.46 0.03 A, an O—O—C angle of 109 2.1° and a M—O—O angle of 112 6.9°. More specialized aspects that deserve to be addressed separately refer to the nature of the M—O bond, the magnitude of the dihedral angle M—O—O—C and the tetrahedral distortion of the peroxide bound C atom. 

In the development of effective catalytic oxidation systems, there is a qualitative correlation between the desirability of the net or terminal oxidant, (OX in equation 1 and DO in equation 2) and the complexity of its chemistry and the difficulty of its use. The desirability of an oxidant is inversely proportional to its cost and directly proportional to the selectivity, rate, and stability of the associated oxidation reaction. The weight % of active oxygen, ease of deployment, and environmental friendliness of the oxidant are also key issues. Pertinent data for representative oxidants are summarized in Table I (4). The most desirable oxidant, in principle, but the one with the most complex chemistry, is O2. The radical chain or autoxidation chemistry inherent in 02-based organic oxidations, whether it is mediated by redox active transition metal ions, nonmetal species, metal oxide surfaces, or other species, is fascinatingly complex and represents nearly a field unto itself (7,75). Although initiation, termination, hydroperoxide breakdown, concentration dependent inhibition... 

Competition between Homolytic and Heterolytic Catalytic Decompositions of Hydroperoxides Reactions of Transition Metals with Free Radicals Reactions of Transition Metal Ions with Dioxygen Catalytic Oxidation of Ketones Cobalt Bromide Catalysis Oscillating Oxidation Reactions... 

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