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铜（I）位点配体增强活性的直接证据。

Direct evidence for ligand-enhanced activity of Cu(i) sites.

作者信息

Dongmo Elvira Gouatieu, Haque Shabnam, Kreuter Florian, Wulf Toshiki, Jin Jiaye, Tonner-Zech Ralf, Heine Thomas, Asmis Knut R

机构信息

Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig Linnéstr. 2 04103 Leipzig Germany

Institute of Resource Ecology, Research Site Leipzig, Helmholtz-Zentrum Dresden-Rossendorf Permoserstr. 15 04318 Leipzig Germany.

出版信息

Chem Sci. 2024 Aug 16;15(36):14635-14643. doi: 10.1039/d4sc04582c. eCollection 2024 Sep 18.

DOI:10.1039/d4sc04582c
PMID:39381432
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11460435/
Abstract

Little is known about the strong mediating effect of the ligand sphere and the coordination geometry on the strength and isotopologue selectivity of hydrogen adsorption on the undercoordinated copper(i) site. Here, we explore this effect using gas-phase complexes Cu(HO)(H) (with ≤ 3) as model systems. Cu(HO) attracts dihydrogen (82 kJ mol ) more strongly than bare Cu (64 kJ mol ) does. Combining experimental and computational methods, we demonstrate a high isotopologue selectivity in dihydrogen binding to Cu(HO), which results from a large difference in the adsorption zero-point energies (2.8 kJ mol between D and H, including an anharmonic contribution of 0.4 kJ mol). We investigate its origins and the bond strengthening between Cu and H upon addition of a single HO ligand. We discuss the role of the environment and the coordination geometry of the adsorption site in achieving a high selectivity and the ramifications for identifying and designing future materials for adsorptive dihydrogen isotopologue separation.

摘要

关于配体球和配位几何结构对低配位铜（I）位点上氢吸附强度和同位素选择性的强烈介导作用，目前所知甚少。在此，我们使用气相配合物Cu(HO)(H) （≤ 3）作为模型系统来探究这种作用。Cu(HO)对氢气的吸引力（82 kJ/mol）比裸铜（64 kJ/mol）更强。结合实验和计算方法，我们证明了氢气与Cu(HO)结合时具有很高的同位素选择性，这是由于吸附零点能存在很大差异（D和H之间为2.8 kJ/mol，包括0.4 kJ/mol的非谐贡献）。我们研究了其起源以及添加单个HO配体后Cu与H之间的键增强情况。我们讨论了吸附位点的环境和配位几何结构在实现高选择性方面的作用以及对识别和设计未来用于吸附性氢气同位素分离材料的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/90f9445d16a1/d4sc04582c-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/d59fa63aa5d7/d4sc04582c-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/11d932d9dfe2/d4sc04582c-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/b83b950a8e8a/d4sc04582c-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/4db91fa8504e/d4sc04582c-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/90f9445d16a1/d4sc04582c-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/d59fa63aa5d7/d4sc04582c-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/11d932d9dfe2/d4sc04582c-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/b83b950a8e8a/d4sc04582c-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/4db91fa8504e/d4sc04582c-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a608/11460435/90f9445d16a1/d4sc04582c-f5.jpg

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Vibrational spectroscopy of Cu(H): about anharmonicity and fluxionality.铜（氢）的振动光谱：关于非谐性和分子内重排
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Strong ortho/para effects in the vibrational spectrum of Cl(H).Cl(H)振动光谱中的强邻位/对位效应。
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Observation of an Intermediate to H Binding in a Metal-Organic Framework.观察金属有机骨架中的中等至强 H 键合。
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