Perfluoroalkylated Arsoranide Salts: Syntheses and Structural Insights

Herein we report the synthesis and structural characterization of perfluoroalkylated arsoranide salts. Complementary quantum chemical calculations provide initial insights into the stability of the corresponding anions. Treatment of As(CF<sub>3</sub>)<sub>2</sub>I and As(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub>X (X = Br, Cl) with the tetraphenylphosphonium halide salts [PPh<sub>4</sub>]X (X = I, Br, Cl) affords the diorganyl arsoranide salts [PPh<sub>4</sub>][As(CF<sub>3</sub>)<sub>2</sub>I<sub>2</sub>] and [PPh<sub>4</sub>][As(C<sub>2</sub>F<sub>5</sub>)X<sub>2</sub>] (X = Br, Cl) in high yields. For the introduction of fluoride ligands, AgF and CsF were employed as fluoride sources. While CsF enables the selective formation of the metal arsoranide salt Cs[As(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub>F<sub>2</sub>], the reaction with AgF results only in a halide exchange. However, in the presence of [PPh<sub>4</sub>]Cl, the corresponding arsoranide salts [PPh<sub>4</sub>][AsR<sub>2</sub>F<sub>2</sub>] (R = CF<sub>3</sub>, C<sub>2</sub>F<sub>5</sub>) are obtained. Treatment of As(CF<sub>3</sub>)I<sub>2</sub> and As(C<sub>2</sub>F<sub>5</sub>)X<sub>2</sub> (X = Br, Cl) with [PPh<sub>4</sub>]X furnishes monoorganyl arsoranide salts [PPh<sub>4</sub>][As(CF<sub>3</sub>)I<sub>3</sub>] and [PPh<sub>4</sub>][As(C<sub>2</sub>F<sub>5</sub>)X<sub>3</sub>] (X = Br, Cl).

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Journal
Inorganic Chemistry
Published
2026-01-16
DOI
https://doi.org/10.1021/acs.inorgchem.5c05249
Primary Topic
Synthesis and characterization of novel inorganic/organometallic compounds
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article
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article

Perfluoroalkylated Arsoranide Salts: Syntheses and Structural Insights

Lukas Hartmann, Hans‐Georg Stammler, Berthold Hoge, Mira Kessler et al.
Inorganic Chemistry
Synthesis and characterization of novel inorganic/organometallic compounds
article

Perfluoroalkylated Arsoranide Salts: Syntheses and Structural Insights

Lukas Hartmann, Hans‐Georg Stammler, Berthold Hoge, Mira Kessler, Claire Simon, Beate Neumann
article en

Abstract

Herein we report the synthesis and structural characterization of perfluoroalkylated arsoranide salts. Complementary quantum chemical calculations provide initial insights into the stability of the corresponding anions. Treatment of As(CF<sub>3</sub>)<sub>2</sub>I and As(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub>X (X = Br, Cl) with the tetraphenylphosphonium halide salts [PPh<sub>4</sub>]X (X = I, Br, Cl) affords the diorganyl arsoranide salts [PPh<sub>4</sub>][As(CF<sub>3</sub>)<sub>2</sub>I<sub>2</sub>] and [PPh<sub>4</sub>][As(C<sub>2</sub>F<sub>5</sub>)X<sub>2</sub>] (X = Br, Cl) in high yields. For the introduction of fluoride ligands, AgF and CsF were employed as fluoride sources. While CsF enables the selective formation of the metal arsoranide salt Cs[As(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub>F<sub>2</sub>], the reaction with AgF results only in a halide exchange. However, in the presence of [PPh<sub>4</sub>]Cl, the corresponding arsoranide salts [PPh<sub>4</sub>][AsR<sub>2</sub>F<sub>2</sub>] (R = CF<sub>3</sub>, C<sub>2</sub>F<sub>5</sub>) are obtained. Treatment of As(CF<sub>3</sub>)I<sub>2</sub> and As(C<sub>2</sub>F<sub>5</sub>)X<sub>2</sub> (X = Br, Cl) with [PPh<sub>4</sub>]X furnishes monoorganyl arsoranide salts [PPh<sub>4</sub>][As(CF<sub>3</sub>)I<sub>3</sub>] and [PPh<sub>4</sub>][As(C<sub>2</sub>F<sub>5</sub>)X<sub>3</sub>] (X = Br, Cl).

Inorganic ChemistryVol. 65(4)
Institute of Molecular Biotechnology (AT), Bell (Canada) (CA), Bielefeld University (DE), Oklahoma State University Oklahoma City (US)
Openalex Percentile: Top 88%
Synthesis and characterization of novel inorganic/organometallic compounds
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Perfluoroalkylated Arsoranide Salts: Syntheses and Structural Insights — Lukas Hartmann, Hans‐Georg Stammler, et al. · Inorganic Chemistry (2026) | TGRS Research Map | TGRS