A new look at molecular and electronic structure of homoleptic diiron(II,II) complexes with N,N-bidentate ligands: Combined experimental and theoretical study
Loading...
Fe-Fe.pdf (1 MB)
Date
2022
Journal Title
Journal ISSN
Volume Title
Publisher
Wiley
Using this material is possible in accordance with the relevant provisions of fair use or other exceptions provided by law. Other use requires the consent of the holder.
Abstract
Paddlewheel-type dinuclear complexes featuring metal–metal bonding have been the subject of widespread interest due to fundamental interest in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N’-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N’-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe2(μ-DPhF)4] structure, a minor alteration in the ligand system, i.e. switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(μ-DTolF)3Fe(κ2-DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, 57Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Interestingly, the Mayer bond orders for the Fe-Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe2(μ-DPhF)4] and [Fe(μ-DTolF)3Fe(κ2-DTolF)], respectively.
Description
This is the pre-peer reviewed version of the following article: K. Korona, M. Terlecki, I. Justyniak, M. Magott, J. Żukrowski, A. Kornowicz, D. Pinkowicz, A. Kubas, J. Lewiński, Chem. Eur. J. 2022, 28, e202200620, which has been published in final form at https://doi.org/10.1002/chem.202200620. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Keywords
Citation
K. Korona, M. Terlecki, I. Justyniak, M. Magott, J. Żukrowski, A. Kornowicz, D. Pinkowicz, A. Kubas, J. Lewiński, Chem. Eur. J. 2022, 28, e202200620. https://doi.org/10.1002/chem.202200620