Rudel Stefan S, Graubner Tim, Karttunen Antti J, Dehnen Stefanie, Kraus Florian
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerweinstrasse 4, Marburg 35032, Germany.
Department of Chemistry and Materials Science, Aalto University, Aalto 00076, Finland.
Inorg Chem. 2021 Oct 4;60(19):15031-15040. doi: 10.1021/acs.inorgchem.1c02532. Epub 2021 Sep 16.
We investigated whether [SiF(NH)] can act as a fluoride-ion acceptor in its reactions with the fluorides F ( = Li-Cs, Tl, NH) in anhydrous liquid ammonia (NH). While LiF and NaF did not react, we obtained the compounds K[SiF(NH)], Rb[SiF(NH)], and Cs[SiF(NH)], as well as [NH(NH)][SiF] and [Tl(NH)][SiF]·2NH, from the other starting materials and characterized them by either single-crystal or powder X-ray diffraction. The compound [NH(NH)][SiF] contains the very rarely observed hydrogen-bonded, -symmetric diammine ammonium cation [NH(NH)], and the compound [Tl(NH)][SiF]·2NH is an example for an uncommon Tl(I)-Tl(I) interaction. This "thallophilic" interaction was investigated with quantum-chemical methods.
我们研究了在无水液氨（NH₃）中，[SiF₅(NH₃)]在与氟化物F⁻（F⁻ = Li⁺ - Cs⁺、Tl⁺、NH₄⁺）反应时是否能作为氟离子受体。虽然LiF和NaF不发生反应，但我们从其他起始原料中得到了化合物K[SiF₅(NH₃)]、Rb[SiF₅(NH₃)]和Cs[SiF₅(NH₃)]，以及[NH₄(NH₃)][SiF₅]和[Tl(NH₃)][SiF₅]·2NH₃，并通过单晶或粉末X射线衍射对它们进行了表征。化合物[NH₄(NH₃)][SiF₅]含有极少见的通过氢键连接的、对称的二胺铵阳离子[NH₄(NH₃)]⁺，化合物[Tl(NH₃)][SiF₅]·2NH₃是一种不常见的Tl(I)-Tl(I)相互作用的实例。用量子化学方法研究了这种“铊亲和性”相互作用。
