Base Induced Dismutation of POCl3 and POBr3
| Autoři | |
|---|---|
| Rok publikování | 2003 |
| Druh | Článek ve sborníku |
| Konference | Euroregionale 2003. Book of Abstracts. |
| Fakulta / Pracoviště MU | |
| Citace | |
| Obor | Anorganická chemie |
| Klíčová slova | Phosphoryl halides; Lewis bases; Dismutation; Donor-stabilized ion |
| Popis | Pyridine does not react with POCl3 when it is free of its hydrolysis products, HCl and HPO2Cl2. DMAP, as a stronger Lewis base, however, reacts readily with POCl3 and yields the crystalline [(DMAP)2PO2]Cl. A 31P NMR study revealed that a base-induced dismutation of POCl3 to PO2Cl and PCl5 occurs in this reaction and the strongly unsaturated PO2Cl is then ligand-stabilized by DMAP as a betaine (DMAP)PO2Cl or a salt of donor-stabilized PO2+ ion, [(DMAP)2PO2]Cl. In contrast to phosphoryl chloride, POBr3 reacts readily with booth DMAP and pyridine to give crystalline [(DMAP)2PO2]Br3 and [(py)2PO2]Br3, respectively. |
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