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

doi:10.1021/acs.inorgchem.1c02532

Reactions of [SiF₄(NH₃)₂] with Fluorides AF (A = Li-Cs, Tl, NH₄) in Liquid NH_3: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

University of Marburg

Research output: Contribution to journal › Article › Scientific › peer-review

2 Citations (Scopus)

135 Downloads (Pure)

Abstract

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, C₂_v-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 language	English
Pages (from-to)	15031–15040
Number of pages	10
Journal	Inorganic Chemistry
Volume	60
Issue number	19
Early online date	16 Sept 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c02532
Publication status	Published - 4 Oct 2021
MoE publication type	A1 Journal article-refereed

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10.1021/acs.inorgchem.1c02532

CHEM_Rudel_et_al_Reactions_of_SiF4NH32_2021_Inorganic_ChemistryAccepted author manuscript, 1.79 MBLicence: Unspecified

Cite this

@article{0e97f88a930c47d3b6303dd4dff8aff7,

title = "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+",

abstract = "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.",

author = "Rudel, \{Stefan S.\} and Tim Graubner and Karttunen, \{Antti J.\} and Stefanie Dehnen and Florian Kraus",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

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doi = "10.1021/acs.inorgchem.1c02532",

language = "English",

volume = "60",

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T1 - 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+

AU - Rudel, Stefan S.

AU - Graubner, Tim

AU - Karttunen, Antti J.

AU - Dehnen, Stefanie

AU - Kraus, Florian

PY - 2021/10/4

Y1 - 2021/10/4

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85115949035

U2 - 10.1021/acs.inorgchem.1c02532

DO - 10.1021/acs.inorgchem.1c02532

M3 - Article

AN - SCOPUS:85115949035

SN - 0020-1669

VL - 60

SP - 15031

EP - 15040

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 19

ER -

Reactions of [SiF₄(NH₃)₂] with Fluorides AF (A = Li-Cs, Tl, NH₄) in Liquid NH_3:A [NH₄(NH₃)₂]⁺Cation and a Thallophilic Interaction in [Tl₂(NH₃)₆]²⁺

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CSD 2079396: Experimental Crystal Structure Determination

CSD 2079397: Experimental Crystal Structure Determination

CCDC 2079398: Experimental Crystal Structure Determination

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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+

Abstract

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Datasets

CSD 2079396: Experimental Crystal Structure Determination

CSD 2079397: Experimental Crystal Structure Determination

CCDC 2079398: Experimental Crystal Structure Determination

Cite this

Reactions of [SiF₄(NH₃)₂] with Fluorides AF (A = Li-Cs, Tl, NH₄) in Liquid NH_3:A [NH₄(NH₃)₂]⁺Cation and a Thallophilic Interaction in [Tl₂(NH₃)₆]²⁺