4148-00-9Relevant academic research and scientific papers
Reversible Ligand-Centered Reduction in Low-Coordinate Iron Formazanate Complexes
Broere, Dani?l L. J.,Mercado, Brandon Q.,Lukens, James T.,Vilbert, Avery C.,Banerjee, Gourab,Lant, Hannah M. C.,Lee, Shin Hee,Bill, Eckhard,Sproules, Stephen,Lancaster, Kyle M.,Holland, Patrick L.
, p. 9417 - 9425 (2018)
Coordination of redox-active ligands to metals is a compelling strategy for making reduced complexes more accessible. In this work, we explore the use of redox-active formazanate ligands in low-coordinate iron chemistry. Reduction of an iron(II) precursor occurs at milder potentials than analogous non-redox-active β-diketiminate complexes, and the reduced three-coordinate formazanate-iron compound is characterized in detail. Structural, spectroscopic, and computational analysis show that the formazanate ligand undergoes reversible ligand-centered reduction to form a formazanate radical dianion in the reduced species. The less negative reduction potential of the reduced low-coordinate iron formazanate complex leads to distinctive reactivity with formation of a new N?I bond that is not seen with the β-diketiminate analogue. Thus, the storage of an electron on the supporting ligand changes the redox potential and enhances certain reactivity.
