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Keywords = planar hexacoordinate metal (phM) clusters

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11 pages, 3601 KiB  
Article
σ-Aromatic MAl6S6 (M = Ni, Pd, Pt) Stars Containing Planar Hexacoordinate Transition Metals
by Li-Xia Bai and Jin-Chang Guo
Molecules 2023, 28(3), 942; https://doi.org/10.3390/molecules28030942 - 17 Jan 2023
Cited by 4 | Viewed by 1864
Abstract
Hypercoordinate transition-metal species are mainly dominated by the 18-valence-electron (18ve) counting. Herein, we report ternary MAl6S6 (M = Ni, Pd, Pt) clusters with the planar hexacoordinate metal (phM) centers, which feature 16ve counting instead of the classic 18ve rule. These [...] Read more.
Hypercoordinate transition-metal species are mainly dominated by the 18-valence-electron (18ve) counting. Herein, we report ternary MAl6S6 (M = Ni, Pd, Pt) clusters with the planar hexacoordinate metal (phM) centers, which feature 16ve counting instead of the classic 18ve rule. These global-minimum clusters are established via unbiased global searches, followed by PBE0 and single-point CCSD(T) calculations. The phM MAl6 units are stabilized by six peripheral bridging S atoms in these star-like species. Chemical bonding analyses reveal that there are 10 delocalized electrons around the phM center, which can render the aromaticity according to the (4n + 2) Hückel rule. It is worth noting that adding an (or two) electron(s) to its π-type lowest unoccupied molecular orbital (LUMO) will make the system unstable. Full article
(This article belongs to the Special Issue DFT Quantum Chemical Calculation of Metal Clusters)
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