H©Cu4I4-: A Planar Tetracoordinate Hydrogen Superhalogen Anion Stabilized by Covalent Multicenter Bonding.

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-30 DOI:10.1021/acs.inorgchem.5c03367

Li-Xia Bai,Ya-Xuan Cheng,Mesías Orozco-Ic,Jin-Chang Guo

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Abstract

Planar tetracoordinate hydrogen (ptH) superhalogen anions are very rare. To date, only a few examples dominated by electrostatic interactions have been reported. Herein, using Cu as the ligands and I as the auxiliary bridges, we computationally design a star-like ptH H©Cu4I4- cluster, which is a global minimum (GM) based on unbiased structural searches, followed by high-level quantum chemical calculations. Born-Oppenheimer molecular dynamics simulations show the resistance of the ptH H©Cu4I4- GM to deformation and isomerization. Chemical bonding analyses reveal that there is one delocalized 5c-2e σ bond over the HCu4 core and four Cu-I-Cu 3c-2e σ bonds along the periphery, except for the lone pairs (LPs). These covalent multicenter bonds dominate the stability of the system rather than aromaticity. Encouragingly, H©Cu4I4- has a high vertical detachment energy (4.74 eV) at the single-point CCSD(T)/def2-TZVPP level and can be viewed as a superhalogen anion. It represents the first covalent bonding dominated ptH superhalogen anion, enriching the ptH chemistry as well as superhalogens.

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H©Cu4I4-：一种共价多中心键稳定的平面四配位超卤素氢阴离子。

平面四配位氢（ptH）超卤素阴离子非常罕见。迄今为止，仅报道了几个以静电相互作用为主的例子。本文以Cu为配体，I为辅助桥，计算设计了一个星形ptH H©Cu4I4-星团，该星团是基于无偏结构搜索的全局最小值（GM），然后进行高阶量子化学计算。Born-Oppenheimer分子动力学模拟显示了ptH H©Cu4I4- GM对变形和异构化的抵抗能力。化学键分析表明，除了孤对外，HCu4核心有1个离域5c-2e σ键，外围有4个Cu-I-Cu 3c-2e σ键。这些共价多中心键决定了体系的稳定性，而不是芳香性。令人鼓舞的是，H©Cu4I4-在单点CCSD(T)/def2-TZVPP水平上具有很高的垂直脱离能（4.74 eV），可以看作是一个超卤素阴离子。它代表了第一个共价键主导的ptH超卤素阴离子，丰富了ptH化学和超卤素。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.