Nucleophilic Reactivity of a Metal-Bound Superoxide Ligand

 

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Abstract

Metal–superoxide species have frequently been implicated as transient intermediates in dioxygen activating metalloenzymes. The metal-bound superoxide moiety has been proposed to react both as an electrophile and a nucleophile. In general, model complexes that mimic metalloenzyme function have been shown to react as electrophiles, and none have displayed nucleophilic reactivity. Herein, we highlight a recent contribution from our group in which we demonstrated the first well-defined example of a metal–superoxide acting as a nucleophile. We have shown the propensity for a copper-superoxide species to perform nucleophilic deformylation of various aldehydes. In doing so, we have provided experimental support for the postulated role of an iron(III)–superoxide reacting as a nucleophile in the α-ketoglutarate-dependent dioxygenases amongst others.

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