Hydroperoxide oxidation:unexpected C-C bond cleavage in branched alkanes and oxidation of molecular nitrogen

摘要

Cyclohexane and C_5-C_(20)n-alkanes undergo oxidation,giving rise to ketones and alcohols in the V~(v)/H_2O_2/AcOH System.The products of oxidation of branched alkanes are indicative of the C-C bond cleavage in these substrates.A number of short-chain ketones,alcohols(and their acetates)were found among the products of isooctane oxidation.A concept is developed,according to which the active oxidant is a vanadium(V)complex containing the coordinated O_3 ~(2-)ligand.The transfer of O atom from the complex to a substrate gives rise to the hydroxylation products.The transfer of O~(+)radical cation from the coordinated O_3 ~(2)ligand is assumed to be responsible for the ketonization or/and C-C bond cleavage.