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Ligand accommodation causes altered reactivity of silver clusters with iodomethane: superatomic stability of Ag9I2+ in mimicking XeF2

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Abstract

Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active sites. Here we report a study of Agn+(n = 1–27) clusters reacting with iodomethane by a flow tube apparatus in tandem with a customized triple quadrupole mass spectrometer. Strong even/odd alternation of the Agn+ is observed in their reactions with CH3I, where silver clusters with even-number, Ag2n+, find favorable products of Ag2nI1,3+ series, while the Ag2n−1+ clusters form Ag2n−1I2,4+ products. Interestingly, Ag9+ shows up with prominent mass abundance but allows for the formation of Ag9I2+, which finds an echo with the formation of Ag10I3+. We illustrate the enhanced stability of Ag9I2+ and Ag10I3+ by showing their significantly enlarged highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps and balanced charge distribution compared with the bare metal clusters, respectively. Also elucidated, is the superatomic nature of these bare and iodinated silver clusters, especially Ag9I2+ which mimics the rare-gas compound XeF2. This study expands a vivid example of special and general superatoms, and enriches the general knowledge on how a ligand stabilizes a metal cluster.

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Acknowledgements

This work was supported by the Ministry of Science and Technology of China (2020YFA0714602), the National Natural Science Foundation of China (21722308, 22003072), and CAS Instrument Development Project (Y5294512C1).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Haiming Wu, Mengzhou Yang, Benben Huang, Wen Gan & Zhixun Luo

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Benben Huang, Wen Gan & Zhixun Luo

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  1. Haiming Wu
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  2. Mengzhou Yang
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  3. Benben Huang
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  4. Wen Gan
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  5. Zhixun Luo
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Correspondence to Zhixun Luo.

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The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Ligand Accommodation Causes Altered Reactivity of Silver Clusters with Iodomethane: Superatomic Stability of Ag9I2+ in Mimicking XeF2

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Wu, H., Yang, M., Huang, B. et al. Ligand accommodation causes altered reactivity of silver clusters with iodomethane: superatomic stability of Ag9I2+ in mimicking XeF2. Sci. China Chem. 65, 1594–1600 (2022). https://doi.org/10.1007/s11426-022-1297-8

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