Davis, M.F., Levason, W., Paterson, J., Reid, G. and Webster, M. (2008) Complexes of Vanadium(V) oxide trifluoride with nitrogen and oxygen donor ligands: Coordination chemistry and some fluorination reactions. European Journal of Inorganic Chemistry, 2008 (5), 802-811. (doi:10.1002/ejic.200701156).
Abstract
[VOF3(MeCN)], obtained by dissolving VOF3 in dry acetonitrile, is a useful synthon for the preparation of complexes of the oxide-fluoride, and the reaction with 2,2-bipyridyl, 1,10-phenanthroline, Me2N(CH2)2NMe2 and Ph2P(O)CH2P(O)Ph2 (L-L), or Ph3PO, Me3PO, Ph3AsO, pyridine and pyridine N-oxide (L), produces the complexes [VOF3(L-L)] or [VOF3(L)2] respectively. These were characterised by microanalysis, IR, UV/Vis and multinuclear NMR [51V, 19F{1H}, 31P{1H}, 1H] spectroscopy, the data showing them to besix-coordinate with trans F-V-F units and the neutralligands trans to O and F, respectively. X-ray crystal structures of [VOF3(1,10-phenanthroline)], [VOF3(Ph3PO)2] and [VOF3(pyNO)2] confirm the geometry, although the first two exhibit O/F disorder trans to the neutral ligand. Unstable complexes with ether and thioether ligands including [VOF3{MeO(CH2)2OMe}], [VOF3{MeS(CH2)2SMe}] and [VOF3(15-crown-5)] are also described; these decompose rapidly even in the solid state, with fluorination of the ligands. The [VOF3(Ph3AsO)2] also decomposes in solutionto a mixture of products including Ph3AsF2 and [V6O12F4(Ph3AsO)2(Ph2AsO2)2] identified crystallographically. Comparisons with complexes of VOCl3 are also described.
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