Base-Induced Dismutation of POCl3 and POBr3: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

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Authors	ROVNANÍK Pavel KAPIČKA Libor TARABA Jan ČERNÍK Miloš
Year of publication	2004
Type	Article in Periodical
Magazine / Source	INORGANIC CHEMISTRY
MU Faculty or unit	Faculty of Science
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]+ .
Related projects:	Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles