Base Induced Dismutation of POCl3 and POBr3

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Authors	ROVNANÍK Pavel ČERNÍK Miloš
Year of publication	2003
Type	Article in Proceedings
Conference	Euroregionale 2003. Book of Abstracts.
MU Faculty or unit	Faculty of Science
Citation
Field	Inorganic chemistry
Keywords	Phosphoryl halides; Lewis bases; Dismutation; Donor-stabilized ion
Description	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.
Related projects:	Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles