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These anions have a sawhorse shape in which the lone pair of the phosphorus atom fills the third equatorial position of the pseudotrigonal bipyramid. Theoretical results show that this association remains incomplete due to strong hydrogen bonding with the cations of the ionic liquid, which competes with the phosphorus trihalide for interaction with the Z<jats:sup>\u2212<\/jats:sup> anion. Temperature\u2010dependent <jats:sup>31<\/jats:sup>P\u2005NMR experiments indicated that the P\u2212Z binding is weaker at higher temperature. Both theory and experiment evidence 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. Detailed knowledge of the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic\u2010liquid mixtures.<\/jats:p>","DOI":"10.1002\/chem.201803558","type":"journal-article","created":{"date-parts":[[2018,8,30]],"date-time":"2018-08-30T05:43:59Z","timestamp":1535607839000},"page":"16323-16331","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Spontaneous Substitutions at Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: Grotthuss Diffusion of Anions?"],"prefix":"10.1002","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3105-7176","authenticated-orcid":false,"given":"Oldamur","family":"Holl\u00f3czki","sequence":"first","affiliation":[{"name":"Mulliken Center for Theoretical Chemistry University of Bonn  Beringstrasse 4+6 53115 Bonn Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander","family":"Wolff","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Technische Universit\u00e4t Dresden  01062 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julia","family":"Pallmann","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Technische Universit\u00e4t Dresden  01062 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rachel E.","family":"Whiteside","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Queen's University of Belfast  Belfast BT7 1NN UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jennifer","family":"Hartley","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry TU Bergakademie Freiberg  09599 Freiberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias A.","family":"Grasser","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Technische Universit\u00e4t Dresden  01062 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peter","family":"Nockemann","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Queen's University of Belfast  Belfast BT7 1NN UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eike","family":"Brunner","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Technische Universit\u00e4t Dresden  01062 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas","family":"Doert","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Technische Universit\u00e4t Dresden  01062 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2391-6025","authenticated-orcid":false,"given":"Michael","family":"Ruck","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry Technische Universit\u00e4t Dresden  01062 Dresden Germany"},{"name":"Max Planck Institute for Chemical Physics of Solids  N\u00f6thnitzer Strasse 40 01187 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,10,24]]},"reference":[{"key":"e_1_2_7_1_1","volume-title":"Chemistry of the Elements","author":"Greenwood N. 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