Five-coordinate MII-semiquinonate (M = Fe, Mn, Co) complexes: Reactivity models of the catechol dioxygenases

Abstract

A series of five-coordinate MII-semiquinonate(M = Fe, Mn, Co) complexes were synthesized and characterized, including the first example of a mononuclear FeII-semiquinonate. Intermediates were observed in the reactions of MII-phenSQ (M = Fe, Co) with O2. Evidence for the relevance of these intermediates to the intradiol catechol dioxygenases was obtained by characterization of the oxidized semiquinone-derived product, muconic anhydride, resulting from the reaction of [PhTttBu]CoII(3,5-DBSQ) with O2. © 2014 The Partner Organisations.