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+

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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2021-10-04

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en

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10

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Inorganic Chemistry, Volume 60, issue 19, pp. 15031–15040

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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.

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Publisher Copyright: © 2021 American Chemical Society.

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Rudel, S S, Graubner, T, Karttunen, A J, Dehnen, S & Kraus, F 2021, ' Reactions of [SiF 4 (NH 3 ) 2 ] with Fluorides AF (A = Li-Cs, Tl, NH 4 ) in Liquid NH 3:  A [NH 4 (NH 3 ) 2 ] +  Cation and a Thallophilic Interaction in [Tl 2 (NH 3 ) 6 ] 2+ ', Inorganic Chemistry, vol. 60, no. 19, pp. 15031–15040 . https://doi.org/10.1021/acs.inorgchem.1c02532