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Complexes of vanadium(IV) oxide difluoride with neutral N- and O-donor ligands

Complexes of vanadium(IV) oxide difluoride with neutral N- and O-donor ligands
Complexes of vanadium(IV) oxide difluoride with neutral N- and O-donor ligands
A convenient new synthesis for complexes of VOF2 with N-donor ligands is via the reaction of VF4 with the ligand in water, either under reflux or using hydrothermal conditions. The complexes, mer-[VOF2(terpy)]·3H2O (terpy = 2,2?6?,2?-terpyridyl), [VOF2(bipy)(H2O)], [VOF2(phen)(H2O)], [VOF2(py)2(H2O)], [VOF2(py)2(H2O)]·H2O, [V2O2F4(py)4] and [pyH]2[V2O2F6(H2O)2], along with the O-donor, pyridine N-oxide (pyNO) complex, [V2O2F4(H2O)2(pyNO)2], have been isolated and characterised. The controlled hydrolysis of VF4 in water produces the hydrate [VOF2(H2O)2]·H2O. The complex [VOF2(Me3tacn)] (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) was prepared by the reaction of [VOF2(py)2(H2O)] and Me3tacn in MeCN. The new complexes have been characterised by microanalysis and single crystal X-ray diffraction. Powder X-ray diffraction (PXRD) data were recorded for the bulk samples and compared with the PXRD patterns simulated from the single crystal data to confirm that the latter were representative of the bulk products. All the complexes contain six-coordinate vanadium(IV), with extensive H-bonding and (in the pyridyl ligand complexes) ?-stacking interactions present. IR and UV–visible spectroscopic data and magnetic measurements are also reported and discussed. Attempts to obtain phosphine oxide or ether complexes by similar routes were unsuccessful. Unless the temperature is carefully controlled, the hydrothermal route yields mixtures of VIV and VV complexes.
0022-1139
149-160
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Furness, Liam
2c50e6af-80f2-40d4-8aca-59843b79b6c1
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Furness, Liam
2c50e6af-80f2-40d4-8aca-59843b79b6c1
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Chang, Yao-Pang, Furness, Liam, Levason, William, Reid, Gillian and Zhang, Wenjian (2016) Complexes of vanadium(IV) oxide difluoride with neutral N- and O-donor ligands. Journal of Fluorine Chemistry, 191, 149-160. (doi:10.1016/j.jfluchem.2016.09.020).

Record type: Article

Abstract

A convenient new synthesis for complexes of VOF2 with N-donor ligands is via the reaction of VF4 with the ligand in water, either under reflux or using hydrothermal conditions. The complexes, mer-[VOF2(terpy)]·3H2O (terpy = 2,2?6?,2?-terpyridyl), [VOF2(bipy)(H2O)], [VOF2(phen)(H2O)], [VOF2(py)2(H2O)], [VOF2(py)2(H2O)]·H2O, [V2O2F4(py)4] and [pyH]2[V2O2F6(H2O)2], along with the O-donor, pyridine N-oxide (pyNO) complex, [V2O2F4(H2O)2(pyNO)2], have been isolated and characterised. The controlled hydrolysis of VF4 in water produces the hydrate [VOF2(H2O)2]·H2O. The complex [VOF2(Me3tacn)] (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) was prepared by the reaction of [VOF2(py)2(H2O)] and Me3tacn in MeCN. The new complexes have been characterised by microanalysis and single crystal X-ray diffraction. Powder X-ray diffraction (PXRD) data were recorded for the bulk samples and compared with the PXRD patterns simulated from the single crystal data to confirm that the latter were representative of the bulk products. All the complexes contain six-coordinate vanadium(IV), with extensive H-bonding and (in the pyridyl ligand complexes) ?-stacking interactions present. IR and UV–visible spectroscopic data and magnetic measurements are also reported and discussed. Attempts to obtain phosphine oxide or ether complexes by similar routes were unsuccessful. Unless the temperature is carefully controlled, the hydrothermal route yields mixtures of VIV and VV complexes.

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Accepted/In Press date: 29 September 2016
e-pub ahead of print date: 5 October 2016
Published date: November 2016
Organisations: Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 404385
URI: https://eprints.soton.ac.uk/id/eprint/404385
ISSN: 0022-1139
PURE UUID: b2bb242d-c99a-43e2-b5f4-aa7f358714a8
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: 09 Jan 2017 09:38
Last modified: 14 Jul 2018 00:37

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Contributors

Author: Yao-Pang Chang
Author: Liam Furness
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Wenjian Zhang

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