Syntheses of Phosphoryl Chloro- and Bromofluorides and Crystal Structures of POFCl2 and POF2Cl
| Authors | |
|---|---|
| Year of publication | 2006 |
| Type | Article in Periodical |
| Magazine / Source | Zeitschrift für Anorganische und Allgemeine Chemie |
| MU Faculty or unit | |
| 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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