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QTAIM view of Fe…Fe binding within triiron clusters [(μ3-S) Fe3(CO)9(μ3-CO)]

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Abstract

The electron density of the [(μ3-S) Fe3(CO)9(μ3-CO)] cluster was analyzed using the quantum theory of atoms in molecules (QTAIM) to explore its topological properties. This analysis provides valuable insight into the interactions between Fe–Fe, Fe–C, and Fe–S as well as other important topological properties of the compounds. Analysis of the core part, especially the S–Fe3–CO region, does not show the presence of bcp (bonding critical points) and bp (bonding pathways) for any pair of M–M (metal–metal) bonds, indicating significant delocalization. There may be multicentric (5c–4e) interactions in the central region of the junction. Examining topological data for Fe–Fe, Fe–S, and Fe–CO bonds, we find that all of these bonds exhibit typical properties of closed-shell metal–metal interactions. However, there is evidence that there is an actual chemical bond between the Fe metal and the carbon atoms of the CO ligand, rather than just an “interaction.” The presence of sulfide-bridging ligands plays an important role in effectively reducing the delocalization of electron density between sulfide-bridged iron pairs as opposed to iron pairs that are not bridging and are coordinated by carbonyl ligands.

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Authors and Affiliations

  1. Department of Chemistry, College of Science, University of Kufa, Najaf, Iraq

    Noorhan Ali Hamza & Muhsen Abood Muhsen Al-Ibadi

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  1. Noorhan Ali Hamza
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  2. Muhsen Abood Muhsen Al-Ibadi
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Contributions

MAMA-I designed the research project, supervised the work, and revised and edited the manuscript, and NAH carried out the calculations and wrote the first draft of the manuscript. All authors contributed to data interpretation and discussion of the results.

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Correspondence to Noorhan Ali Hamza.

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Hamza, N.A., Al-Ibadi, M.A.M. QTAIM view of Fe…Fe binding within triiron clusters [(μ3-S) Fe3(CO)9(μ3-CO)]. Theor Chem Acc 142, 120 (2023). https://doi.org/10.1007/s00214-023-03065-x

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