Oxidation of alkanes and alcohols with hydrogen peroxide catalyzed by complex Os₃(CO)₁₀(µ‐H)₂

Abstract

Abstract Trinuclear carbonyl hydride cluster, Os 3 (CO) 10 (µ‐H) 2 , catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by hydrogen peroxide in acetonitrile solution. The hydroperoxide partly decomposes in the course of the reaction to afford cyclooctanone and cyclooctanol. Selectivity parameters obtained in oxidations of various linear and branched alkanes as well as kinetic features of the reaction indicated that the alkane oxidation occurs with the participation of hydroxyl radicals. A similar mechanism operates in transformation of benzene into phenol and styrene into benzaldehyde. The system also oxidizes 1‐phenylethanol to acetophenone. The kinetic study led to a conclusion that oxidation of alcohols does not involve hydroxyl radicals as main oxidizing species and apparently proceeds with the participation of osmyl species, ‘OsO’. Copyright © 2010 John Wiley & Sons, Ltd.