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

Synthesis, chemistry and structures of complexes of the dioxovanadium(V) halides VO2F and VO2Cl
Synthesis, chemistry and structures of complexes of the dioxovanadium(V) halides VO2F and VO2Cl
[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].
0300-9246
6265-6273
Davis, Martin F.
72f26f03-4bbe-482e-b8a5-6c792b22fcc3
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Leung, Alethea
916d04ce-c0ec-436f-9ce9-a33e9f776851
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Littlefield, Benjamin
85284530-7e72-406a-aee8-a1fa1bfa8190
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Davis, Martin F.
72f26f03-4bbe-482e-b8a5-6c792b22fcc3
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Leung, Alethea
916d04ce-c0ec-436f-9ce9-a33e9f776851
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Littlefield, Benjamin
85284530-7e72-406a-aee8-a1fa1bfa8190
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

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).

Record type: Article

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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Published date: 2008

Identifiers

Local EPrints ID: 146985
URI: http://eprints.soton.ac.uk/id/eprint/146985
ISSN: 0300-9246
PURE UUID: b397ffae-e8ff-44d9-bded-ba88fcea4b81
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 23 Apr 2010 08:23
Last modified: 29 Oct 2019 02:11

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