Initiation Of Autoxidation Research Articles

Iron–molybdenum-oxo complexes as initiators for olefin autoxidation with O2

The reaction between [(TPA)Fe(MeCN)2](OTf)2 and [nBu4N](Cp*MoO3) yields the novel tetranuclear complex [(TPA)Fe(μ-Cp*MoO3)]2(OTf)2, 1, with a rectangular [Mo-O-Fe-O-]2 core containing high-spin iron(ii) centres. 1 proved to be an efficient initiator/(pre)catalyst for the autoxidation of cis-cyclooctene with O2 to give cyclooctene epoxide. To test, which features of 1 are essential in this regard, analogues with zinc(ii) and cobalt(ii) central atoms, namely [(TPA)Zn(Cp*MoO3)](OTf), 3, and [(TPA)Co(Cp*MoO3)](OTf), 4, were prepared, which proved to be inactive. The precursor compounds of 1, [(TPA)Fe(MeCN)2](OTf)2 and [nBu4N](Cp*MoO3) as well as Cp2*Mo2O5, were found to be inactive, too. Reactivity studies in the absence of cyclooctene revealed that 1 reacts both with O2 and PhIO via loss of the Cp* ligands to give the triflate salt 2 of the known cation [((TPA)Fe)2(μ-O)(μ-MoO4)](2+). The cobalt analogue 4 reacts with O2 in a different way yielding [((TPA)Co)2(μ-Mo2O8)](OTf)2, 5, featuring a Mo2O8(4-) structural unit which is novel in coordination chemistry. The compound [(TPA)Fe(μ-MoO4)]2, 6, being related to 1, but lacking Cp* ligands failed to trigger autoxidation of cyclooctene. However, initiation of autoxidation by Cp* radicals was excluded via experiments including thermal dissociation of Cp2*.

Novel role for tropospheric ozone in initiation of autoxidation

The views on initiation of autoxidation of organic materials need considerable revision. In the past 50 years, autoxidation of organic materials has been attributed to chain reactions initiated by the decomposition of hydroperoxides contained in the substrate. It is found that, initiation of polyolefin oxidation is caused much more by the ozone contained in the atmosphere. The accumulated ozone exposure is determining the length of the induction period and, therefore, to a large extent the overall thermal oxidative lifetime of polymers. It is assumed that it is also valid for other organic materials including biologically important molecules.

The antioxidant activity of alpha-tocopherol-bovine serum albumin complex in micellar and liposome autoxidations.

A comparison is made of the antioxidant activity of a water-soluble form of alpha-tocopherol complexed with bovine serum albumin (alpha-T X BSA) with that of micellar alpha-tocopherol and aqueous 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylate (Trolox) to inhibit autoxidation of linoleic acid in sodium dodecyl sulfate micelles. The peroxyl radical trapping ability of alpha-T X BSA compares favorably with that of alpha-tocopherol and Trolox, and all three can be used in quantitative measurements of the susceptibility of the micellar substrate to undergo autoxidation: the oxidizability, for reactions initiated in the micellar phase by di-tertbutylhyponitrite (DBHN) or in the aqueous phase by azobisamidinopropane hydrochloride (ABAP). alpha-Tocopherol and Trolox are also effective antioxidants to inhibit DBHN- or ABAP-initiated autoxidations of dilinoleoylphosphatidylcholine (DLPC) liposomes prepared as multilamellar or unilamellar bilayers characterized by 31P NMR spectra. The oxidizability of DLPC liposomes is determined by various combinations of water-soluble and lipid-soluble initiators and the antioxidants, alpha-tocopherol and Trolox. In contrast, alpha-T X BSA does not effectively trap peroxyl radicals when it is added after initiation of autoxidation in the lipid phase (DBHN) or in the aqueous phase (ABAP). The radical trapping ability of alpha-T X BSA becomes evident if it is mixed with the DLPC for some hours before initiation. This result is interpreted in terms of diffusion of alpha-tocopherol from the bound alpha-T X BSA form to the liposome before it exhibits antioxidant activity.

The aerobic oxidation of unsaturated fatty acids and their esters: cobalt stearate-catalyzed oxidation of linoleic acid

SUMMARY The connection between metal catalysis and the initiation step in autoxidation is emphasized. The formation of free radicals occurs in reactions involving not only various valency states, but also oxygen-complexes of the catalyst. The kinetics of the initial phase of the metal-catalyzed aerobic oxidation of linoleic acid are examined in detail, and a number of mechanisms postulated. The rate constants for certain initiation reactions are evaluated together with the corresponding activatian energies. The observed values are found to be in fair agreement with theoretical considerations and, in general, the evidence lends further support to the hypothesis that trace-metal catalysis and the initiation of autoxidation are intimately connected.