A Crystalline Tri-thorium Cluster with σ-Aromatic Metal-Metal Bonding - Nature.com

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Abstract

Metal-metal bonding is a widely studied area of chemistry^1–3, and has become a mature field spanning numerous d transition metal and main group complexes^4–7. In contrast, actinide-actinide bonding is predicted to be weak⁸, being currently restricted to spectroscopically-detected gas-phase U₂ and Th₂^9,10, U₂H₂ and U₂H₄ in frozen matrices at 6-7 Kelvin (K)^11,12, or fullerene-encapsulated U₂¹³. Conversely, attempts to prepare thorium-thorium bonds in frozen matrices produced only ThH_n (n = 1-4)¹⁴. Thus, there are no isolable actinide-actinide bonds under normal conditions. Computational investigations have explored the likely nature of actinide-actinide bonding¹⁵, concentrating on localised σ-, π-, and δ-bonding models paralleling d transition metal analogues, but predictions in relativistic regimes are challenging and have remained experimentally unverified. Here, we report thorium-thorium bonding in a crystalline cluster, prepared and isolated under normal experimental conditions. The cluster exhibits a diamagnetic, closed-shell singlet ground-state with a valence-delocalised three-centre-two-electron σ-aromatic bond^16,17 that is counter to the focus of previous theoretical predictions. The experimental discovery of actinide σ-aromatic bonding adds to main group and d transition metal analogues, extending delocalised σ-aromatic bonding to the heaviest elements in the periodic table and to principal quantum number six, and constitutes a new approach to elaborating actinide-actinide bonding.

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Affiliations

Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK

Josef T. Boronski, John A. Seed, Adam W. Woodward, Ashley J. Wooles, Louise S. Natrajan, Nikolas Kaltsoyannis & Stephen T. Liddle
Institute of Physical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569, Stuttgart, Germany

David Hunger & Joris van Slageren

Authors

Josef T. Boronski

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John A. Seed

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David Hunger

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Adam W. Woodward

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Joris van Slageren

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Ashley J. Wooles

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Louise S. Natrajan

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Nikolas Kaltsoyannis

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Stephen T. Liddle

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Corresponding authors

Correspondence to Nikolas Kaltsoyannis or Stephen T. Liddle.

Supplementary information

Supplementary Data Table S1

Final single point energy and coordinates for geometry optimised 3'.

Supplementary Data Table S2

Final single point energy and coordinates for geometry optimised 3"

Supplementary Data Table S3

Final single point energy and coordinates for geometry optimised [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃K₂]²⁺.

Supplementary Data Table S4

Final single point energy and coordinates for geometry optimised [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃].

Supplementary Data Table S5

Final single point energy and coordinates for geometry optimised [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃H]^–.

Supplementary Data Table S6

Final single point energy and coordinates for geometry optimised [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃K₂H]⁺.

Supplementary Data Table S7

Final single point energy and coordinates for geometry optimised [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃K₂H].

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Boronski, J.T., Seed, J.A., Hunger, D. et al. A Crystalline Tri-thorium Cluster with σ-Aromatic Metal-Metal Bonding. Nature (2021). https://ift.tt/3gqvqxB

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Received: 07 December 2020
Accepted: 06 August 2021
Published: 23 August 2021
DOI: https://doi.org/10.1038/s41586-021-03888-3

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A Crystalline Tri-thorium Cluster with σ-Aromatic Metal-Metal Bonding - Nature.com
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