Spontaneous Substitutions on Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: A Grotthuss Diffusion of Anions?

Oldamur Holloczki, Alexander Wolff, Julia Pallmann, Rachel Whiteside, Jennifer Hartley, Matthias A Grasser, Peter Nockemann, Eike Brunner, Thomas Doert, Michael Ruck

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Abstract

PX3 species (X = Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z = Cl, Br, I) of the solvent, forming [PX3Z] complex anions. These anions are found to have a sawhorse shape, with the lone pair of the phosphorus atom filling the third equatorial position of the pseudo trigonal bipyramid. Theoretical results show that this association remains incomplete due to the strong hydrogen bonding with the ionic liquid cations, which competes with the phosphorus trihalide for the interactions with the Z- anion. Temperature-dependent 31P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiments evidence a dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. The detailed knowledge on the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic liquid mixtures.

Original languageEnglish
JournalChemistry - A European Journal
Early online date29 Aug 2018
DOIs
Publication statusEarly online date - 29 Aug 2018

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Ionic Liquids
Ionic liquids
Phosphorus
Anions
Substitution reactions
Negative ions
Atoms
Ion exchange
Halogens
Cations
Hydrogen bonds
Positive ions
Experiments
Ligands
Nuclear magnetic resonance
Association reactions
Temperature

Cite this

Holloczki, Oldamur ; Wolff, Alexander ; Pallmann, Julia ; Whiteside, Rachel ; Hartley, Jennifer ; Grasser, Matthias A ; Nockemann, Peter ; Brunner, Eike ; Doert, Thomas ; Ruck, Michael. / Spontaneous Substitutions on Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: A Grotthuss Diffusion of Anions?. In: Chemistry - A European Journal. 2018.
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title = "Spontaneous Substitutions on Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: A Grotthuss Diffusion of Anions?",
abstract = "PX3 species (X = Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z = Cl, Br, I) of the solvent, forming [PX3Z] complex anions. These anions are found to have a sawhorse shape, with the lone pair of the phosphorus atom filling the third equatorial position of the pseudo trigonal bipyramid. Theoretical results show that this association remains incomplete due to the strong hydrogen bonding with the ionic liquid cations, which competes with the phosphorus trihalide for the interactions with the Z- anion. Temperature-dependent 31P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiments evidence a dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. The detailed knowledge on the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic liquid mixtures.",
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Spontaneous Substitutions on Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: A Grotthuss Diffusion of Anions? / Holloczki, Oldamur; Wolff, Alexander; Pallmann, Julia; Whiteside, Rachel; Hartley, Jennifer; Grasser, Matthias A; Nockemann, Peter; Brunner, Eike; Doert, Thomas; Ruck, Michael.

In: Chemistry - A European Journal, 29.08.2018.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Spontaneous Substitutions on Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: A Grotthuss Diffusion of Anions?

AU - Holloczki, Oldamur

AU - Wolff, Alexander

AU - Pallmann, Julia

AU - Whiteside, Rachel

AU - Hartley, Jennifer

AU - Grasser, Matthias A

AU - Nockemann, Peter

AU - Brunner, Eike

AU - Doert, Thomas

AU - Ruck, Michael

N1 - © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2018/8/29

Y1 - 2018/8/29

N2 - PX3 species (X = Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z = Cl, Br, I) of the solvent, forming [PX3Z] complex anions. These anions are found to have a sawhorse shape, with the lone pair of the phosphorus atom filling the third equatorial position of the pseudo trigonal bipyramid. Theoretical results show that this association remains incomplete due to the strong hydrogen bonding with the ionic liquid cations, which competes with the phosphorus trihalide for the interactions with the Z- anion. Temperature-dependent 31P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiments evidence a dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. The detailed knowledge on the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic liquid mixtures.

AB - PX3 species (X = Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z = Cl, Br, I) of the solvent, forming [PX3Z] complex anions. These anions are found to have a sawhorse shape, with the lone pair of the phosphorus atom filling the third equatorial position of the pseudo trigonal bipyramid. Theoretical results show that this association remains incomplete due to the strong hydrogen bonding with the ionic liquid cations, which competes with the phosphorus trihalide for the interactions with the Z- anion. Temperature-dependent 31P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiments evidence a dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. The detailed knowledge on the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic liquid mixtures.

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