Issue 15, 2024

Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

Abstract

Compounds containing Mn–O bonds are of utmost importance in biological systems and catalytic processes. Nevertheless, mononuclear manganese complexes containing all O-donor ligands are still rare. Taking advantage of the low tendency of the pentafluoroorthotellurate ligand (teflate, OTeF5) to bridge metal centers, we have synthesized two homoleptic manganese complexes with monomeric structures and an all O-donor coordination sphere. The tetrahedrally distorted MnII anion, [Mn(OTeF5)4]2−, can be described as a high spin d5 complex (S = 5/2), as found experimentally (magnetic susceptibility measurements and EPR spectroscopy) and using theoretical calculations (DFT and CASSCF/NEVPT2). The high spin d4 electronic configuration (S = 2) of the MnIII anion, [Mn(OTeF5)5]2−, was also determined experimentally and theoretically, and a square pyramidal geometry was found to be the most stable one for this complex. Finally, the bonding situation in both complexes was investigated by means of the Interacting Quantum Atoms (IQA) methodology and compared to that of hypothetical mononuclear fluoromanganates. Within each pair of [MnXn]2− (n = 4, 5) species (X = OTeF5, F), the Mn–X interaction is found to be comparable, therefore proving that the similar electronic properties of the teflate and the fluoride are also responsible for the stabilization of these unique species.

Graphical abstract: Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

Supplementary files

Article information

Article type
Edge Article
Submitted
23 yan 2024
Accepted
26 fev 2024
First published
05 mar 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 5564-5572

Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands

A. Pérez-Bitrián, J. Munárriz, K. B. Krause, J. Schlögl, K. F. Hoffmann, J. S. Sturm, A. N. Hadi, C. Teutloff, A. Wiesner, C. Limberg and S. Riedel, Chem. Sci., 2024, 15, 5564 DOI: 10.1039/D4SC00543K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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