Synthesis, chemistry and structures of complexes of the dioxovanadium(V) halides VO2F and VO2Cl

Davis, Martin F., Jura, Marek, Leung, Alethea, Levason, William, Littlefield, Benjamin, Reid, Gillian and Webster, Michael (2008) Synthesis, chemistry and structures of complexes of the dioxovanadium(V) halides VO2F and VO2Cl. Dalton Transactions, 44, 6265-6273. (doi:10.1039/b811422f).

Abstract

[VO2F(L–L)] (L–L = 2,2-bipyridyl, 1,10-phenanthroline, Me2N(CH2)2NMe2) and [VO2F(py)2] (py = pyridine) have been prepared from the corresponding [VOF3(L–L)] or [VOF3(py)2] and O(SiMe3)2 in MeCN solution. VO2F (itself made from VOF3 and O(SiMe3)2 in MeCN) forms [Me4N][VO2F2] with [Me4N]F, but does not react with neutral N- or O-donor ligands. VO2Cl, prepared from VOCl3 and ozone, reacts with 2,2-bipyridyl or 1,10-phenanthroline to form [VO2Cl(L–L)], with pyridine or pyridine-N-oxide (L) to produce [VO2Cl(L)2], and with OPPh3 or OAsPh3 (L) gives [VO2Cl(L)]. A second product from the OPPh3 system is the ionic [VO2(OPPh3)3][VO2Cl2] containing a trigonal bipyramidal cation. Neither VO2F nor VO2Cl form isolable complexes with MeCN, thf or MeO(CH2)2OMe, and both are reduced by P-, As-, S- or Se-donor ligands. [Ph4As][VO2X2] (X = F or Cl) react with 2,2-bipyridyl to form [VO2X(2,2-bipyridyl)], but similar reactions with weaker O-donor ligands fail. The complexes have been characterised by IR, multinuclear NMR (1H, 19F, 51V or 31P) and UV-visible spectroscopy. X-ray crystal structures are reported for [VO2F(py)2], [VO2Cl(L)2] (L = py or pyNO) and [VO2(OPPh3)3][VO2Cl2].

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Contributors

Author: William Levason

Author: Gillian Reid

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