Alkyl hydroperoxides self-alkylation

Recently, we have developed a versatile aqueous medium self-assembly method for the generation of diverse multicopper(II) complexes and coordination polymers derived from cheap and commercially available ligands such as aminoalcohols and benzenecarboxylates [6-15]. The obtained compounds were applied as highly efficient and versatile catalysts or catalyst precursors in two different alkane functionalization reactions. These include the mild oxidation of alkanes (typically cyclohexane as a model substrate) by hydrogen peroxide into alkyl hydroperoxides, alcohols, and ketones [6-9, 11, 16, 17], as well as the hydrocarboxylation of gaseous and liquid C ( = 2 - 9) alkanes, by carbon monoxide, water, and potassium peroxodisulfate into the corresponding carboxylic acids [12-15, 18-22]. 

The alkyl radical formed in the initial oxidation reactions subsequently react with O2 resulting in the formation of alkylperoxy radical. The alkylperoxy radical is the key intermediate in the oxidation of VOCs by OH radical and further reacts with HO2, NO2 and NO in the atmosphere. This intermediate can also undergo self-reaction and epoxidation reactions. These reactions lead to the formation of hydroperoxide adducts, alkoxy radical and O3, and also OH radical regeneration. The alkoxy radical is the second key intermediate in the VOCs oxidation by OH radical. The alkoxy radical undergoes prompt decomposition resulting in the oxidation of NO. The characterization of these secondary reactions is studied extensively using theoretical methods, but only very few experimental studies are available for such reactions. 

Alkyl and peroxyl radicals alternating lead the chain process. Therefore, oxidation can be retarded by acceptors of both alkyl and peroxyl radicals. Autooxidation develops as a self-initiated ROOH forming chain reaction. Hence, autooxidation can be retarded by the decomposition of hydroperoxide or decreasing the rate of its decomposition to radicals. According to the corrqrlicated oxidation mechanism, inhibitors in mechanism of their action can be divided into the following six groups. 

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