A crystalline tri-thorium cluster with σ-aromatic metal-metal bonding.

Autor: Boronski JT; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK., Seed JA; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK., Hunger D; Institute of Physical Chemistry, University of Stuttgart, Stuttgart, Germany., Woodward AW; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK., van Slageren J; Institute of Physical Chemistry, University of Stuttgart, Stuttgart, Germany., Wooles AJ; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK., Natrajan LS; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK., Kaltsoyannis N; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK. nikolas.kaltsoyannis@manchester.ac.uk., Liddle ST; Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, UK. steve.liddle@manchester.ac.uk.
Jazyk: angličtina
Zdroj: Nature [Nature] 2021 Oct; Vol. 598 (7879), pp. 72-75. Date of Electronic Publication: 2021 Aug 23.
DOI: 10.1038/s41586-021-03888-3
Abstrakt: 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 . By contrast, actinide-actinide bonding, which is predicted to be weak 8 , is currently restricted to spectroscopically detected gas-phase U 2 and Th 2 (refs. 9,10 ), U 2 H 2 and U 2 H 4 in frozen matrices at 6-7 K (refs. 11,12 ), or fullerene-encapsulated U 2 (ref. 13 ). Furthermore, attempts to prepare thorium-thorium bonds in frozen matrices have produced only ThH n (n = 1-4) 14 . Thus, there are no isolable actinide-actinide bonds under normal conditions. Computational investigations have explored the probable nature of actinide-actinide bonding 15 , concentrating on localized 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-delocalized 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 delocalized σ-aromatic bonding to the heaviest elements in the periodic table and to principal quantum number six, and constitutes a new approach to elaborate actinide-actinide bonding.
(© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)
Databáze: MEDLINE
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