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Reversible Ligand‐Centered Reduction in Low‐Coordinate Iron Formazanate Complexes
Author(s) -
Broere Daniël 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.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801298
Subject(s) - redox , ligand (biochemistry) , chemistry , reactivity (psychology) , non innocent ligand , crystallography , photochemistry , stereochemistry , inorganic chemistry , receptor , biochemistry , medicine , alternative medicine , pathology
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.