title: Enhancing the deperoxidation activity of cobalt(II)acetylacetonate by the addition of octanoic acid.
abstract: The homolytic scission of peroxides with catalytic amounts of cobalt(II) complexes is used in several industrial oxidation processes. In this contribution, we report that addition of small amounts of octanoic acid significantly enhances the catalytic deperoxidation activity of the cobalt(II)acetylacetonate complex. We attribute this to the stabilization of the Co--OOR bond upon coordination of octanoic acid, preventing the unimolecular scission. As such, the cobalt peroxo intermediate is forced to enter an alternative catalytic cycle which causes its rapid conversion to the highly reactive cobalt hydroxy. This shift in catalytic cycle results in a higher pre-exponential rate factor, over-compensating the higher barrier of the new rate-determining step.
authors.affiliation: Department of Chemistry and Applied Bio-Sciences, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich (Switzerland).
authors.forename: Eyal
authors.initials: E
authors.lastname: Spier
authors.forename: Ive
authors.initials: I
authors.lastname: Hermans
keywords: cobalt; deactivation; homogeneous catalysis; kinetics; oxidation mechanisms