Publication details
Base-Induced Dismutation of POCl3 and POBr3: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations
| Authors | |
|---|---|
| Year of publication | 2004 |
| Type | Article in Periodical |
| Magazine / Source | INORGANIC CHEMISTRY |
| MU Faculty or unit | |
| Citation | |
| Field | Inorganic chemistry |
| Keywords | Phosphoryl halides; Lewis bases; Donor-acceptor systems; Cations; N-ligands; DFT calculations |
| Description | The interaction between POCl3 or POBr3 and pyridine or DMAP has been reinvestigated to clarify the discrepancies between previously published results concerning the Lewis acidity of phosphoryl halides and their behavior toward pyridine bases. The obtained results show that POCl3 virtually does not react with pyridine, while it does with 4-(dimethylamino)pyridine (DMAP), even in SO2 solution, to yield an ionic compound [(DMAP)2PO2]Cl.3SO2 (1.3SO2). Its recrystallization from acetonitrile gives [(DMAP)2PO2]Cl.CH3CN (1.CH3CN). The POBr3 reacts readily with both DMAP and pyridine forming the analogous tribromides, [(DMAP)2PO2]Br3 (2) and [(py)2PO2]Br3 (3),respectively. The crystal structures of 1.CH3CN,1.3SO2, 2, and 4 revealed that all four compounds are ionic containing the distorted tetrahedral cations [(DMAP)2PO2]+ and [(py)2PO2]+ . |
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