Syntheses of Phosphoryl Chloro- and Bromofluorides and Crystal Structures of POFCl2 and POF2Cl

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Authors

ROVNANÍK Pavel ŽÁK Zdirad ČERNÍK Miloš

Year of publication 2006
Type Article in Periodical
Magazine / Source Zeitschrift für Anorganische und Allgemeine Chemie
MU Faculty or unit

Faculty of Science

Citation
Field Inorganic chemistry
Keywords Phosphorus; Fluorides; Crystal structure; Intermolecular association; Phosphoryl fluorohalides
Description A simple procedure for the preparation of phosphoryl chlorofluorides, POFCl2 and POF2Cl, by chlorination of the appropriate potassium fluorophosphates, K2PO3F and KPO2F2, respectively, with PCl5 is described. The analogous bromination with PBr5 gives POFBr2 and POF2Br. However, due to low yields and high content of impurities, this method is not suitable for the synthesis of the former compound. Both chlorofluorides were crystallized from the melt at low temperatures and their crystal structures were determined by X-ray diffraction at 120 K. Distorted tetrahedral molecules of POFCl2 are only weakly associated through intermolecular O-Cl contacts forming infinite chains similarly as in crystalline POCl3. In POF2Cl, however, the chains are formed by the O-P contacts, and an additional P-OC-l bridging leads to their linkage into a double-chain structure.
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