Alkali Cation Effects on Redox-Active Formazanate Ligands in Iron Chemistry

Noncovalent interactions of organic moieties with Lewis acidic alkali cations can greatly affect structure and reactivity. Herein, we describe the effects of interactions with alkali-metal cations within a series of reduced iron complexes bearing a redox-active formazanate ligand, in terms of structures, magnetism, spectroscopy, and reaction rates. In the absence of a crown ether to sequester the alkali cation, dimeric complexes are isolated wherein the formazanate has rearranged to form a five-membered metallacycle. The dissociation of these dimers is dependent on the binding mode and size of the alkali cation. In the dimers, the formazanate ligands are radical dianions, as shown by X-ray absorption spectroscopy, Mössbauer spectroscopy, and analysis of metrical parameters. These experimental measures are complemented by density functional theory calculations that show the spin density on the bridging ligands.