Abstract
1. In alkaline (the oxidation of methanol) and in neutral media (the oxidation of cumene) the catalysis by copper complexes of o-phenantroline is due to the formation in the system of Cu(I)(o-Ph), which is capable of coordinating oxygen to form the charge-transfer complex Cu(II)(o-Ph)n·O2·. 2. In neutral media the oxidation proceeds by a pathway involving the interaction of Cu(II)(o-Ph)nO2· with the hydrocarbon according to a bimolecular mechanism and then according to the usual free-radical chain mechanism with quadratic chain termination. The oxidation of methanol in alkaline medium apparently proceeds according to an intrasphere mechanism owing to the coordination of CH3OH and O2 without the release of radicals into the bulk.
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