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Updated: Sep 25, 2025

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Published on: July 27, 2022
Metal-centered monocyclic carbon wheel clusters with record coordination numbers in planar species
Xiao-Qin Lu1, Hai-Gang Lu1, Si-Dian Li1
1Nanocluster Laboratory, Institute of Molecular Science, Shanxi University Taiyuan 030006 China luhg@sxu.edu.cn lisidian@sxu.edu.cn.
Abstract:
The highest coordination number identified to date in planar species is CN = 10 in metal-centered monocyclic boron wheel clusters D 10h M©B10 - (M = Ta and Nb) (Galeev et. al., Angew. Chem. Int. Ed., 2012, 51, 2101). Extensive global minimum searches and first-principles theory calculations performed herein indicate that the experimentally observed LaC13 + and LaC14 + possess the well-defined global minima of perfect metal-centered monocyclic carbon wheel D 13h La©C13 + (1) and slightly off-centered C 2v La©C14 + (4) (1A1) with record coordination numbers of CN = 13 and 11 in planar structures, respectively, further pushing the boundary of our understanding of chemical structures and bonding. Detailed molecular orbital, nucleus-independent chemical shift, and ring current analyses indicate that D 13h La©C13 + (1) is σ + π dually aromatic in nature, with 14 totally delocalized in-plane σ electrons and 14 totally delocalized out-of-plane π electrons each matching the 4N + 2 aromatic rule (N σ = N π = 3). Similar σ + π dually aromatic metal-centered monocyclic wheel clusters D 13h Ca©C13 (2), C 13v Ac©C13 + (3), C 2v Y©B6C6 + (5), and C 2v Sc©B5C6 (6) have also been obtained with CN = 13, 13, 12, and 11, respectively. The results obtained in this work effectively enrich the chemical structures and bonding patterns of planar hypercoordinated complexes.
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