Investigating f-block metal-metal bonding by quantum crystallography
- Florian Meurer
- Talk , Chemistry
- TBC
- TBC
Florian Meurera, Stephen T. Liddleb, and Michael Bodensteinera
aUniversity of Regensburg, 93053 Regensburg, Germany. bThe University of Manchester, Manchester, M13 9PL, UK.
e-mail: florian.meurer@ur.de
Metal-metal bonding plays a central role in explaining the structure and reactivity of compounds all across the periodic table. So far, the heaviest metal-metal interaction described by quantum crystallographical methods was an Au–Au metallophilic interaction.[1] In this work, we want to present our advances of quantum crystallography into actinide-actinide bonding at the hands of two recently found Th3 clusters (see Figure 1a, [2,3]), one of which is a dianion, the other a monoanion. Hirshfeld-Atom-Refinement (HAR, [4,5]) was employed to get an accurate structure of both clusters and compare the results to in vacuo optimised density functional theory (DFT).
The deformation density (Figure 1c) as well as the topological analysis of the total electron density (Figure 1b and d) based on HAR, reveal a 3c2e and 3c1e Th–Th–Th interaction with distinct bond paths and a negative Laplacian area in the middle of the Th3 ring.
Structure (a) and evaluation of the [Th3Cl6]2– dianion (left) and the [Th3Cl6]– monoanion (right) concerning the Laplacian of the total electron density (b), the deformation density (c), and the electron localizability index (ELI-D) for each cluster, respectively.
To compare the results obtained from the HAR geometry DFT calculation with the experiment, beyond the strong artifacts common for heavy element structures, we employed difference residual density maps.
At the ICDM10, I want to discuss this kind of map and whether they are suitable for use in these cases, or not.
References:
[1] S. Pawlȩdzio, M. Malinska, F. Kleemiss, S. Grabowsky, K. Woźniak, Inorg. Chem. 2022, 61, 4235–4239.
[2] J. T. Boronski, J. A. Seed, D. Hunger, A. W. Woodward, J. van Slageren, A. J. Wooles, L. S. Natrajan, N. Kaltsoyannis, S. T. Liddle, Nature 2021, 598, 72–75.
[3] J. A. Seed, X. Deng, J. Tomeček, A. Brookfield, D. Collison, F. Tuna, A. J. Wooles, G. F. S. Whitehead, N. Kaltsoyannis, S. T. Liddle, Nat. Chem. 2025, 1–7.
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