Publication details
Base Induced Dismutation of POCl3 and POBr3
| Authors | |
|---|---|
| Year of publication | 2003 |
| Type | Article in Proceedings |
| Conference | Euroregionale 2003. Book of Abstracts. |
| MU Faculty or unit | |
| 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. |
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