Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

[VOF 3 (MeCN)], obtained by dissolving VOF 3 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, Me 2 N(CH 2 ) 2 NMe 2 and Ph 2 P(O)CH 2 P(O)Ph 2 (L–L), or Ph 3 PO, Me 3 PO, Ph 3 AsO, pyridine and pyridine N ‐oxide (L), produces the complexes [VOF 3 (L–L)] or [VOF 3 (L) 2 ] respectively. These were characterised by microanalysis, IR, UV/Vis and multinuclear NMR [ 51 V, 19 F{ 1 H}, 31 P{ 1 H}, 1 H] 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 [VOF 3 (1,10‐phenanthroline)], [VOF 3 (Ph 3 PO) 2 ] and [VOF 3 (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 [VOF 3 {MeO(CH 2 ) 2 OMe}], [VOF 3 {MeS(CH 2 ) 2 SMe}] and [VOF 3 (15‐crown‐5)] are also described; these decompose rapidly even in the solid state, with fluorination of the ligands. The [VOF 3 (Ph 3 AsO) 2 ] also decomposes in solutionto a mixture of products including Ph 3 AsF 2 and [V 6 O 12 F 4 (Ph 3 AsO) 2 (Ph 2 AsO 2 ) 2 ] identified crystallographically. Comparisons with complexes of VOCl 3 are also described.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)