Catalytic activity of a dinuclear manganese-based complex [Mn-2(IV)(mu-O)(3)L-2](PF6)(2) (MnMeTACN) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane), and its combination with a polyamine, 1, 1,4,7, 10, 10-hexamethyltriethylenetetramine (HMTETA), was investigated on the oxidation of ethyl linoleate (EL). When MnMeTACN was molecularly mixed with EL in a co-solvent (methanol), MnMeTACN alone was found to be a very active catalyst for the oxidation of unpurifed EL (containing a small amount of hydroperoxides), similar to the catalytic activity of a Co-based catalyst. For purified EL (free of hydroperoxides), the addition of tert-butyl hydroperoxide was necessary to rapidly initiate the EL oxidation. A tentative catalytic cycle for MnMeTACN was proposed on the basis of electrospray ionization mass spectrometry (ESI-MS) investigation. The existence of HMTETA significantly accelerated the decomposition of the formed hydroperoxides into alkoxy free radicals, which in turn led to a high level of volatile aldehyde byproducts due to beta-scission reactions. (c) 2006 Elsevier B.V. All rights reserved.