A Crystalline Tri-thorium Cluster: When Metal σ-Aromaticity Just Isn’t Enough

Very recently, Liddle and coworkers extended the range of aromaticity to a record seventh row of the periodic table by successful isolation of the crystalline actinide cluster 3 containing at its heart the σ-aromatic tri-thorium ring. In this study we prove that the authors have misinterpreted the experimental Raman spectrum of 3, which eventually led to the wrong conclusions about the role of the σ-aromatic tri-thorium bonding in the synthesized cluster. We demonstrate that the thorium-thorium bond in 3 is not very different from the already known extremely weak actinide-actinide bonds, and the marginal σ-aromatic stabilization in the Th3 ring makes it hardly distinguishable from ordinary non-aromatic rings. Also, we show that the multicenter charge-shift bonding in the Th3Cl6 cage is a vital factor that determines the uniqueness and remarkable thermodynamic stability of 3. By clarifying the misleading conclusions of the original Nature paper and drawing special attention to the essential stabilizing role of actinide-halogen charge-shift bonding, this study may have broader implications for understanding the chemistry of actinides and future attempts to design and synthesize new stable actinide complexes.