Reversible Ligand-Centered Reduction in Low-Coordinate Iron Formazanate Complexes.

ABSTRACT: 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 ?-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 ?-diketiminate analogue. Thus, the storage of an electron on the supporting ligand changes the redox potential and enhances certain reactivity.

SUBMITTER: Broere DLJ 

PROVIDER: S-EPMC6115202 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature