Issue 27, 2025

Assessing structure and dynamics of iron complexes supported by tris(amidate)amine ligands

Abstract

Chelating ligand platforms derived from tris(2-aminoethyl)amine (TREN) can facilitate low coordination numbers and provide opportunities to tune the steric and electronic profile of the secondary coordination sphere. Herein, we examine the ability of two related tris(amidate)amine ligands to stabilize low-coordinate complexes of trivalent iron, and further use molecular dynamics (MD) simulations to gain insight into the dynamics of both the primary and secondary coordination spheres. Our cavitand-inspired ligand allows for the isolation of four-coordinate FeLOCH2Ovia oxidation of the anionic and isostructural ferrous precursor, demonstrating how the secondary sphere macrocycle can promote the retention of an open coordination site. Through comparison with a non-macrocyclized tris(amidate)amine ligand, molecular dynamics (MD) simulations are used to garner insights into how this macrocycle alters coordination sphere dynamics. Additionally, both four-coordinate FeLOCH2O and five-coordinate Fe(DMF)LOMe are shown to be synthons for the trigonal bipyramidal ferric fluoride complexes [Fe(F)LOCH2O] and [Fe(F)LOMe], respectively.

Graphical abstract: Assessing structure and dynamics of iron complexes supported by tris(amidate)amine ligands

Supplementary files

Article information

Article type
Paper
Submitted
31 May 2025
Accepted
18 Jun 2025
First published
19 Jun 2025

Dalton Trans., 2025,54, 10719-10724

Assessing structure and dynamics of iron complexes supported by tris(amidate)amine ligands

L. S. X. Huffman, A. Seshadri, C. D. Hastings, W. W. Brennessel, I. Franco and B. R. Barnett, Dalton Trans., 2025, 54, 10719 DOI: 10.1039/D5DT01284H

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