Tomeček Josef, Liddle Stephen T, Kaltsoyannis Nikolas
Department of Chemistry and Centre for Radiochemistry Research, School of Natural Sciences, The University of Manchester, Oxford Road, Manchester, UK.
Chemphyschem. 2023 Sep 15;24(18):e202300366. doi: 10.1002/cphc.202300366. Epub 2023 Aug 4.
The tri-thorium cluster [{Th(η -C H )(μ -Cl) } {K(THF) } ] (Nature 2021, 598, 72-75) was reported to feature intriguing σ-aromatic bonding between the thorium atoms, a mode of metal-metal bonding unique in the actinide series. However, the presence of this bonding motif has since been challenged by others. Here, we computationally explore electron delocalisation in a molecular cluster fragment of [{Th(η -C H )(μ -Cl) } {K(THF) } ] and examine its responses to an applied magnetic field using a variety of methods. We also discuss the importance of the choice of basis set for the Th atoms and issues regarding locating QTAIM bond critical points. When taken together, the computed data consistently suggest the presence of delocalised Th-Th bonding and Th σ-aromaticity.
据报道，三钍簇合物[{Th(η⁵-C₅H₅)(μ-Cl)}₂{K(THF)₆}]（《自然》，2021年，第598卷，第72 - 75页）在钍原子之间具有引人注目的σ芳香键，这是锕系元素系列中独特的金属 - 金属键合模式。然而，此后这种键合模式的存在受到了其他人的质疑。在这里，我们通过计算探索[{Th(η⁵-C₅H₅)(μ-Cl)}₂{K(THF)₆}]分子簇片段中的电子离域，并使用多种方法研究其对施加磁场的响应。我们还讨论了钍原子基组选择的重要性以及关于定位QTAIM键临界点的问题。综合来看，计算数据一致表明存在离域的Th - Th键合和Th σ芳香性。
