σ-Aromatic MAl₆S₆ (M = Ni, Pd, Pt) Stars Containing Planar Hexacoordinate Transition Metals.

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 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 unoccupi

SUBMITTER: Bai LX 

PROVIDER: S-EPMC9920543 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature