Synthesis and Electronic Structure of Neutral Square-Planar High-Spin Iron(II) Complexes Supported by a Dianionic...

Two square-planar high-spin Fe^II complexes bearing a dianionic pyridine dipyrrolate pincer ligand and a diethyl ether or tetrahydrofuran ligand were synthesized and structurally characterized, and their electronic structures were elucidated by a combined spectroscopic and computational approach. In contrast to previous examples, the S = 2 ground states of these square-planar Fe^II complexes do not require an overall anionic charge of the compounds or incorporation of alkali metal cations. The tetrahydrofuran complex exhibits an equilibrium between four- and five-coordinate species in solution, which was supported by ¹H NMR and ⁵⁷Fe Mössbauer spectroscopy and comparison to a structurally characterized five-coordinate pyridine dipyrrolate iron bis-pyridine adduct. A detailed computational analysis of the electronic structures of the four- and five-coordinate species via density functional theory provides insight into the origins of the unusual ground state configurations for Fe^II in a square-planar ligand field and explains the associated characteristic spectroscopic parameters.