Reactions of [SiF4(NH3)2] with Fluorides AF (A = Li-Cs, Tl, NH4) in Liquid NH3: A [NH4(NH3)2]Cation and a Thallophilic Interaction in [Tl2(NH3)6]2+

Stefan S. Rudel, Tim Graubner, Antti J. Karttunen, Stefanie Dehnen, Florian Kraus*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review


We investigated whether [SiF4(NH3)2] can act as a fluoride-ion acceptor in its reactions with the fluorides AF (A = Li-Cs, Tl, NH4) in anhydrous liquid ammonia (NH3). While LiF and NaF did not react, we obtained the compounds K[SiF5(NH3)], Rb[SiF5(NH3)], and Cs[SiF5(NH3)], as well as [NH4(NH3)2]2[SiF6] and [Tl2(NH3)6][SiF6]·2NH3, from the other starting materials and characterized them by either single-crystal or powder X-ray diffraction. The compound [NH4(NH3)2]2[SiF6] contains the very rarely observed hydrogen-bonded, C2v-symmetric diammine ammonium cation [NH4(NH3)2]+, and the compound [Tl2(NH3)6][SiF6]·2NH3 is an example for an uncommon Tl(I)-Tl(I) interaction. This "thallophilic" interaction was investigated with quantum-chemical methods.

Original languageEnglish
Pages (from-to)15031–15040
Number of pages10
JournalInorganic Chemistry
Issue number19
Early online date16 Sep 2021
Publication statusPublished - 4 Oct 2021
MoE publication typeA1 Journal article-refereed


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