Activation of alkyl hydroperoxides by manganese complexes of tmtacn for initiation of radical polymerisation of alkenes.

The activation of alkyl hydroperoxides to generate radicals is a key step in the initiation of radical polymerisations in many industrial applications, not least protective coatings. Cobalt soaps (Co(ii) alkyl carboxylates) are highly effective catalysts under ambient conditions but viable alternatives based on less scarce catalysts are desirable, with especially iron and manganese catalysts showing potential. Manganese complexes of the ligand ,',″-trimethyl-1,4,7-triazacyclononane (tmtacn) are long established as catalysts for organic oxidations with HO, however their reactivity with alkyl hydroperoxides is less studied especially in apolar solvents.

Formation of substituted dioxanes in the oxidation of gum arabic with periodate.

Renewable polysaccharide feedstocks are of interest in bio-based food packaging, coatings and hydrogels. Their physical properties often need to be tuned by chemical modification, by oxidation using periodate, to introduce carboxylic acid, ketone or aldehyde functional groups. The reproducibility required for application on an industrial scale, however, is challenged by uncertainty about the composition of product mixtures obtained and of the precise structural changes that the reaction with periodate induces.