Autoxidation homolytic mechanisms

Homolytic autoxidations of hydrocarbons often give complex mixtures of products-the autoxidation of olefins is a prime example. There is a great incentive, therefore, to search for catalysts that can promote the selective oxidation of olefins by essentially nonradical mechanisms. For example, there is no method available for carrying out the selective epoxidation or oxidative cleavage of olefins (see Section III.C) by molecular oxygen. In order to be successful, any heterolytic pathway for the metal-catalyzed oxidation of a substrate must, of course, be considerably faster than the ubiquitous homolytic processes for autoxidation. Thus, the metal catalysts discussed in the following sections, in addition to being able to promote heterolytic oxidations, are also able to catalyze homolytic processes. 

Kinetics and mechanism—homolytic processes, oxidation, autoxidation, organo-metallic peroxides... 

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