期刊
NATURE
卷 598, 期 7879, 页码 72-+出版社
NATURE PORTFOLIO
DOI: 10.1038/s41586-021-03888-3
关键词
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资金
- UK Engineering and Physical Sciences Research Council [EP/K024000/1, EP/M027015/1, EP/P001386/1, EP/S033181/1, EP/T011289/1]
- Natural Environment Research Council [NE/R011230/1]
- European Research Council [CoG612724]
- Royal Society [UF110005]
- Deutsche Forschungsgemeinschaft [SL104/10-1]
- Landesgraduiertenforderung of the State of Baden-Wurttemberg
- University of Manchester
- Alexander von Humboldt Foundation
- NERC [NE/R011230/1] Funding Source: UKRI
Actinide-actinide bonding is typically predicted to be weak and difficult to observe under normal conditions, but the experimental discovery of thorium-thorium bonding in a crystalline cluster has revealed a new type of sigma-aromatic bond that challenges previous theoretical predictions. This discovery extends delocalized sigma-aromatic bonding to the heaviest elements in the periodic table and offers a new approach to studying actinide-actinide bonding.
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)), U2H2 and U2H4 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 ThHn (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 sigma-, pi-, and delta-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 sigma-aromatic bond(16,17) that is counter to the focus of previous theoretical predictions. The experimental discovery of actinide sigma-aromatic bonding adds to main group and d transition metal analogues, extending delocalized sigma-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.
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