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Complexes of Vanadium(V) oxide trifluoride with nitrogen and oxygen donor ligands: Coordination chemistry and some fluorination reactions

Complexes of Vanadium(V) oxide trifluoride with nitrogen and oxygen donor ligands: Coordination chemistry and some fluorination reactions
Complexes of Vanadium(V) oxide trifluoride with nitrogen and oxygen donor ligands: Coordination chemistry and some fluorination reactions
[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.
oxide-fluorides, crystal-structure, oxytrifluoride, x-ray, stereochemistry, derivatives, difluoride, cl, fluoride, vanadium complexes, elements
1434-1948
802-811
Davis, M.F.
22d05b77-e973-4ca6-9148-bf63a99c6316
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Paterson, J.
b6d85117-51f3-4ba4-b105-6c3c304a1805
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, M.
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Davis, M.F.
22d05b77-e973-4ca6-9148-bf63a99c6316
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Paterson, J.
b6d85117-51f3-4ba4-b105-6c3c304a1805
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, M.
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

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).

Record type: Article

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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Submitted date: 25 October 2007
Published date: 2008
Keywords: oxide-fluorides, crystal-structure, oxytrifluoride, x-ray, stereochemistry, derivatives, difluoride, cl, fluoride, vanadium complexes, elements

Identifiers

Local EPrints ID: 54440
URI: http://eprints.soton.ac.uk/id/eprint/54440
ISSN: 1434-1948
PURE UUID: 28868236-76c6-4306-96df-fd9ac0260ee7
ORCID for W. Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for G. Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 06 Aug 2008
Last modified: 26 Nov 2019 02:07

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Contributors

Author: M.F. Davis
Author: W. Levason ORCID iD
Author: J. Paterson
Author: G. Reid ORCID iD
Author: M. Webster

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