Redox-active ligands coordinated to transition metal ions can serve as electron reservoirs due to their ability to access multiple oxidation states.  A new series of mononuclear [ONOq]FeX2 complexes, where [ONOq]-1 is the quinonate form of the redox-active ligand [ONOcat]-3 shown in Scheme 1, have been prepared and characterized.  Reactivity studies of the [ONOq]FeX2 family of complexes reveal a proclivity for oxidation-reduction reactivity. The reaction of [ONOq]FeX2 with N,N'-diphenylhydrazine resulted in the elimination of HX and the formation of the diazene and an iron-containing product.  This iron-containing product is a bimetallic complex, Fe2[ONO]3, containing one five-coordinate and one six-coordinate iron centers.  The presence of three redox-active [ONO] ligands coordinating the diiron core leads to rich redox chemistry.  The combination of unique structural and electronic factors in Fe2[ONO]3 presents an interesting platform for  small-molecule activation reactivity.  The results of structural, spectroscopic, and electrochemical studies of this new family of compounds will be discussed.  Scheme 1.     Oxidation and reduction of [ONO] ligand platform.

Iron complexes of the redox-active [ONO] ligand

243rd National Meeting (2012)

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