Concentric Inner 2π/6σ and Outer 10π/14σ Aromaticity Underlies the Dynamic Structural Fluxionality of Planar B19 – Wankel Motor Cluster

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 125; no. 23; pp. 5022 - 5030
• Main Authors: Li, Rui, You, Xue-Rui, Guo, Jin-Chang, Zhai, Hua-Jin
• Format: Journal Article
• Language: English
• Published: American Chemical Society 17.06.2021
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.1c02764

Planar C 2v B19 – global-minimum (GM) cluster is known as a molecular Wankel motor, featuring unique chemical bonding and structural fluxionality. While the geometry, bonding, and molecular dynamics of the cluster are documented in the literature, it remains warranted to fully understand its bonding nature and unravel the mechanism behind the structural dynamics. We shall offer herein an updated bonding model on the bases of canonical molecular orbital (CMO) analysis and adaptive natural density partitioning (AdNDP), further aided by natural bond orbital (NBO) analysis and orbital composition calculations. The computational data indicate that the B19 – cluster has inner 2π/6σ and outer 10π/14σ concentric 4-fold π/σ aromaticity. Being spatially isolated from each other, the inner B6 disk supports 2π and 6σ subsystems, whereas the outer B18 double-ring ribbon has 10π and 14σ subsystems. All 4-fold π/σ subsystems are intrinsically delocalized and conform to the (4n + 2) Hückel rule for aromaticity. The change of Wiberg bond index (WBI) from GM to transition-state (TS) for radial B–B links is minimal and uniform, which offers a semiquantitative measure of structural dynamics and underlies the low energy barrier.