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Reactivity and Controlled Redox Reactions of Salt-like Intermetallic Compounds in Imidazolium-Based Ionic Liquids

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Feng,  Xian-Juan
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Schmidt,  Marcus
Marcus Schmidt, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Baitinger,  Michael
Michael Baitinger, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Grin,  Yuri
Juri Grin, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Böhme,  Bodo
Bodo Böhme, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Feng, X.-J., Lerch, S., Biller, H., Micksch, M., Schmidt, M., Baitinger, M., et al. (2021). Reactivity and Controlled Redox Reactions of Salt-like Intermetallic Compounds in Imidazolium-Based Ionic Liquids. ChemistryOpen, 10, 1-12. doi:10.1002/open.202000262.


Cite as: http://hdl.handle.net/21.11116/0000-0007-E49B-9
Abstract
Substituted imidazolium ionic liquids (ILs) were investigated for their reactivity towards Na12Ge17 as a model system containing redox-sensitive Zintl cluster anions. The ILs proved widely inert for imidazolium cations with a 1,2,3-trisubstitution at least by alkyl groups, and for the anion bis(trifluoromethylsulfonyl)azanide (TFSI). A minute conversion of Na12Ge17 observed on long-time contact with such ILs was not caused by dissolution of the salt-like compound, and did thus not provide dissolved Ge clusters. Rather, a cation exchange led to the transfer of Na+ ions into solution. In contrast, by using benzophenone as an oxidizer, heterogeneous redox reactions of Na12Ge17 were initiated, transferring a considerable part of Na+ into solution. At optimized conditions, an X-ray amorphous product NaGe6.25 was obtained, which was thermally convertible to the crystalline type-II clathrate Na24–δGe136 with almost completely Na-filled polyhedral cages, and α-Ge. The presented method thus provides unexpected access to Na24–δGe136 in bulk quantities. © 2021 The Authors. Published by Wiley-VCH GmbH