In:
New Journal of Chemistry, Royal Society of Chemistry (RSC), Vol. 47, No. 6 ( 2023), p. 2736-2746
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 BeB 12 + cluster, in which the Be atom is located above one side of a B 12 tube. It can be formally formulated as a charge transfer [Be] 2+ [B 12 ] − complex, with minimal covalent interaction between the Be atom and B 12 tube. The [B 12 ] − 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 BeB 12 0/− clusters featured quasi-planar/planar geometries. The neutral BeB 12 cluster was structurally robust and dynamically nonfluxional with an insurmountable rotational energy barrier. Chemical bonding analysis revealed that anionic BeB 12 − has 7π and 10σ delocalization. In particular, this series of BeB 12 +/0/− clusters is isoelectronic with Li n B 12 ( 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.
Type of Medium:
Online Resource
ISSN:
1144-0546
,
1369-9261
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2023
detail.hit.zdb_id:
1472933-7
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