Competition between Hydrogen and Chalcogen Bonding in Homodimers of Chalcogen Hydrides (H2X)2, X = O, S, Se, Te

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-03-21 DOI:10.1021/jacs.4c17428

Maxwell P. Hoffman, Sotiris S. Xantheas

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Abstract

The structural and chemical bonding motifs manifested by the competition between hydrogen and chalcogen bonding in the homodimers of chalcogen hydrides (H₂X)₂, where X = O, S, Se, Te have been characterized using high-level electronic structure calculations and analysis of the electron density based on Quasi-atomic orbital (QUAO) and the Symmetry-adapted perturbation theory (SAPT) methods. The QUAO analysis clearly identifies a three-center interaction responsible for either hydrogen or chalcogen bonds: in the former, the σ-bond connecting the donor and hydrogen atom participating in the hydrogen bond interacts with the lone pair on the nucleophile acceptor via the hydrogen atom, while in the latter this same σ-bond interacts with the nucleophile lone pair via the donor chalcogen. The number of minimum energy structures increase dramatically from one for (H₂O)₂, three for (H₂S)₂, four for (H₂Se)₂, and finally six for (H₂Te)₂. The emergence of the chalcogen-bonded arrangements appears for (H₂S)₂ with their subsequent energetic stabilization over the hydrogen-bonded minima manifesting in (H₂Se)₂ and (H₂Te)₂. In particular, one of the (H₂S)₂ , two of the (H₂Se)₂, and three of the (H₂Te)₂ dimers are chalcogen bonded. Induction plays a small but important role in stabilizing hydrogen over chalcogen-bonded structures, while dispersion is more important for chalcogen bonds.

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氢氢化物（H2X）同型二聚体中氢、硫键的竞争2，X = 0， S, Se, Te

采用基于准原子轨道（QUAO）和对称自适应摄动理论（SAPT）的高能级电子结构计算和电子密度分析方法，对氢氢化物（H2X）2同型二聚体（X = O， S, Se, Te）中氢和硫键竞争所表现的结构和化学键基序进行了表征。QUAO分析清楚地确定了氢键或硫键的三中心相互作用：在前者中，连接给体和参与氢键的氢原子的σ键通过氢原子与亲核试剂受体上的孤对相互作用，而在后者中，相同的σ键通过给体硫与亲核试剂的孤对相互作用。最小能量结构的数量从（H2O）2的1个，（H2S）2的3个，（H2Se）2的4个，到（H2Te）2的6个显著增加。（H2S）2中出现了硫键排列，随后在（H2Se）2和（H2Te）2中出现了氢键最小值的能量稳定。特别地，一个（H2S）2，两个（H2Se）2和三个（H2Te）2二聚体是氯键的。诱导对稳定氢在碳键结构上的作用虽小但很重要，而色散对碳键的稳定作用更重要。

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

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.