A crystalline tri-thorium cluster: σ-aromaticity vs charge-shift bonding

Very recently, Boronski et al. reported the first thorium-thorium bond in a crystalline cluster prepared under normal experimental conditions. By using a range of experimental techniques and computational models, the authors found that the isolated actinide cluster contains at its heart two paired electrons delocalized over the tri-thorium ring. The recorded Raman spectrum allegedly confirmed the existence of a σ-aromatic three-center two-electron bond. In the following we demonstrate that the experimentally observed broad inelastic scattering bands between 60 and 135 cm-1, originally assigned by the authors to thorium-thorium vibrations, represent the combination of Th–Cl stretching and Th–Cl–Th bending modes, and they establish the existence of an unprecedented multicenter charge-shift bonding (ThCl2)3 rather than the σ-aromatic bonding Th3. In the light of the presented findings, the latter remains experimentally unproven and computationally questionable.