Effective and Catalytic Reduction of Perchlorate by Atom Transfer–Reaction Kinetics and Mechanisms

Abstract

The reaction kinetics and mechanisms of catalytic reduction of perchlorate and chlorate ions by organic thioethers are described. Oxazoline and thiazoline oxorhenium complexes serve as efficient catalysts for the reduction of perchlorate under mild conditions by a pure oxygen atom transfer mechanism. The observed rate law features saturation kinetics with respect to oxo donor (perchlorate or chlorate) concentration. The factors that make this new family of catalytsts effective and viable have been delineated including different pathways of catalyst deactivation and inhibition. Comparisons to other transition metal complexes that do react controllably with perchlorate are presented.