Donor-Stabilized Dioxophosphonium Cation: Synthesis, Hydrolysis and Crystal Structure of [(DMAP)2PO2]Cl.CH3CN

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Authors	ROVNANÍK Pavel ČERNÍK Miloš
Year of publication	2002
Type	Article in Proceedings
Conference	Sborník příspěvků IV. seminář Pokroky v anorganické chemii
MU Faculty or unit	Faculty of Science
Citation
Field	Inorganic chemistry
Keywords	Cations; donor-acceptor complexes; N-ligands; dioxophosphonium; crystal structures
Description	The reaction of POCl3 with strong basic 4-dimethylaminopyridine /DMAP/ in liquid SO2 produces a white solid that could be recrystallized from acetonitrile. The single-crystal structure determination revealed an ionic structure of bis(4-dimethylaminopyridine)dioxophosphonium chloride solvated by one molecule of acetonitrile.It can be considered a salt of donor-stabilised PO2+ ion,an hitherto unknown analogue of the nitronium cation,NO2+. A 31P NMR spectroscopic study showed a significant difference between the acid and alkali hydrolysis of [(DMAP)2PO2]+ ion and enabled to propose the corresponding reaction mechanism.
Related projects:	Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles