硼基反三明治Ta2B6团簇的化学成键模型

刘芳林 , 翟华金

山西大学学报(自然科学版) ›› 2025, Vol. 48 ›› Issue (04) : 775 -783.

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山西大学学报(自然科学版) ›› 2025, Vol. 48 ›› Issue (04) : 775 -783. DOI: 10.13451/j.sxu.ns.2024067
化学

硼基反三明治Ta2B6团簇的化学成键模型

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Chemical Bonding of Boron-based Inverse Sandwich Ta2B6 Cluster Revisited

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摘要

硼基反三明治团簇是一类新型复合团簇。团簇Ta2B6是其中一个典型体系,已报道的化学成键图像存在缺陷。本文运用一系列现代化学键分析工具详尽地研究团簇Ta2B6的化学成键和芳香性。研究结果表明:该团簇具有6π/6σ双重芳香性,它们均符合休克尔(4n+2)电子计数规则。该结论区别于文献中相关的12π/4σ电子计数。每个Ta中心保留2个近似非键5d电子,但不是孤对。团簇中没有显著的金属间相互作用。同时,团簇中B-B骨架σ键显示一定程度的棱形Ta-B2-Ta四中心两电子特征,而不是经典路易斯两中心两电子键,这种成键现象在分子体系中是鲜见的。本工作提出的成键模型有望拓展至其他反三明治团簇体系。

Abstract

Boron-based inverse sandwich clusters are a new class of compound systems, for which D6h Ta2B6 cluster is a typical example. However, the existing chemical bonding model of inverse sandwich Ta2B6 cluster has fundamental flaws and an indepth revisiting of the system is warranted. In this work, chemical bonding and aromaticity of Ta2B6 cluster are studied computationally using an array of modern quantum chemistry tools, which include canonical molecular orbital (CMO) analysis, adaptive natural density partitioning (AdNDP), electron localization functions (ELFs), and nucleus-independent chemical shifts (NICSs). The concerted results reveal 6π/6σ double aromaticity in the cluster, conforming to the (4n + 2) Hückel rule. The observation differs distinctly from the prior 12π/4σ electron counting in the literature. Each Ta center maintains two 5d electrons that are essentially nonbonding, albeit they do not form a lone pair. There is not direct Ta Ta bonding in the system. The skeleton σ framework along B6 ring is shown to possess a certain extent of rhombic Ta B2 Ta four-center two-electron (4c-2e) character. It does not have strict Lewis-type σ single bonds, which is rare in molecular systems. The present bonding model may be extended to other inverse sandwich clusters.

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关键词

硼基B-Ta合金团簇 / 反三明治团簇 / 化学键 / 双重π/σ芳香性 / 适应性自然密度划分

Key words

boron-based BTa alloy clusters / inverse sandwich clusters / chemical bonding / double π/σ aromaticity / adaptive natural density partitioning (AdNDP)

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刘芳林,翟华金. 硼基反三明治Ta2B6团簇的化学成键模型[J]. 山西大学学报(自然科学版), 2025, 48(04): 775-783 DOI:10.13451/j.sxu.ns.2024067

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基金资助

国家自然科学基金(21873058)

国家自然科学基金(21573138)

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