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The formation of byproducts during the Co(acac)2and Cr(acac)3-catalyzed cyclohexane autoxidation is compared with the noncatalyzed thermal process. CoIIions seem to cause only a moderate perturbation of the reaction mechanism, causing a fast conversion of the cyclohexyl hydroperoxide via a redox cycle, rather than via abstraction of the H-atom by chain carrying peroxyl radicals. Nevertheless, both the radical propagation and the CoII-induced decomposition of the hydroperoxide cause the formation of cyclohexoxy radicals that are partially transformed to 6-hydroxyhexanoic acid, the major primary byproduct for these systems. However, during the CoII-catalyzed reaction, the concentration of cyclohexanone increases much faster than that of the hydroperoxide, causing the ketone to take over the role of dominant byproduct source. A mechanism for the conversion of cyclohexanone to ring-opened byproducts is put forward. Cr(acac)3seems to catalyze additional reactions, some of them probably leading directly to byproducts. Indeed, the evolution of (by)products is significantly different from the CoII-catalyzed and the thermal systems, in the sense that they all seem to be primary in origin. [ABSTRACT FROM AUTHOR]