Influence of the molecular weight of ionenes on the cobaltphthalocyanine-catalysed autoxidation of mercaptoethanol

In order to study the promoting effect of polycations on the cobalt(II)phthalocyanine-tetrasodiumsulphonate (CoPc(NaSO₃)₄)-catalysed autoxidation of thiols, it is imperative to know the molecular weight dependence of the polymer. Monodisperse oligomers can often supply a lot of information. To elecidate the mechanism of the promoting effect of 2,4-ionene, a poly(quaternary ammonium)salt, on the CoPc(NaSO₃)₄-catalysed autoxidation of 2-mercaptoethanol, a series of monodisperse 2,4-ionene oligomers were prepared. Trimeric 2,4-ionenes, containing two quaternary ammonium groups separated by four methylene groups, showed a high co-catalytic activity, and active Co-aggregates were detected with visible light spectroscopy. The spectroscopic behaviour was in close agreement with that of high molecular 2,4-ionene/CoPc(NaSO₃)₄ complexes. In order to achieve this aggregation several oligomeric ionenes have to act concertedly. If the distance between the ionic sites is short the trimer acts as a simple salt in stablizing the aggregates. With respect to the catalytic activity the optimum polycation/catalyst ratio, expressed as the N⁺/Co ratio, decreased with increasing chain lenght and reached a constant level of 50 at a 2,4-ionene nonamer. For the trimers and pentamers this ratio is affected by the type of end-group. All synthesized 2,4-ionene oligomers exhibited excellent co-catalytic properties at the optimum N⁺/Co ratio, with maximum turnover frequencies of 4600 mol thiol/(mol Co s), i.e. 50 times higher than those obtained for the polymer-free system. In the case of monodisperse 2,4-ionene pentamer with bromo end-groups, double Michaelis–Menten kinetics were observed, as also was exhibited by high molecular weight ionene.