Issue 6, 2023

Boron-based tubular BeB12+ and quasi-planar BeB120/− clusters: structural transformation and chemical bonding

Abstract

Boron is electron deficient and has strong bonding capacity, and thus it has given rise to several boron-based clusters with unique geometric structures and bonding properties. Inspired by the contemporary boron double-ring clusters, we are designing a tubular boron cluster doped with alkaline earth metals, which are considered promising ligands. Herein, we present a double-ring tubular BeB12+ cluster, in which the Be atom is located above one side of a B12 tube. It can be formally formulated as a charge transfer [Be]2+[B12] complex, with minimal covalent interaction between the Be atom and B12 tube. The [B12] tube is more stable than the quasi-planar configuration because of three-fold π/σ aromaticity and optimal electrostatic interaction. After sequential reduction, a structural transformation occurs dramatically changing from tubular shape to quasi-planar. The neutral and anionic BeB120/− clusters featured quasi-planar/planar geometries. The neutral BeB12 cluster was structurally robust and dynamically nonfluxional with an insurmountable rotational energy barrier. Chemical bonding analysis revealed that anionic BeB12 has 7π and 10σ delocalization. In particular, this series of BeB12+/0/− clusters is isoelectronic with LinB12 (n = 1–3) reported by Merino. However, they exhibit significantly different geometries due to the differences in electrostatic interaction. Therefore, optimal electrostatic interactions can tune the energetic preference between tubular and quasi-planar/planar structures.

Graphical abstract: Boron-based tubular BeB12+ and quasi-planar BeB120/− clusters: structural transformation and chemical bonding

Supplementary files

Article information

Article type
Paper
Submitted
10 Oct 2022
Accepted
19 Dec 2022
First published
20 Dec 2022

New J. Chem., 2023,47, 2736-2746

Boron-based tubular BeB12+ and quasi-planar BeB120/− clusters: structural transformation and chemical bonding

L. Feng, Y. Wang, X. Hu, C. Miao, M. Yan and Y. Gao, New J. Chem., 2023, 47, 2736 DOI: 10.1039/D2NJ04951A

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