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.
149-160
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Furness, Liam
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Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
November 2016
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, .
(doi:10.1016/j.jfluchem.2016.09.020).
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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VOF2 ms 17_09_2016 revised final.pdf
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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
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Local EPrints ID: 404385
URI: http://eprints.soton.ac.uk/id/eprint/404385
ISSN: 0022-1139
PURE UUID: b2bb242d-c99a-43e2-b5f4-aa7f358714a8
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Date deposited: 09 Jan 2017 09:38
Last modified: 16 Mar 2024 02:43
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Author:
Yao-Pang Chang
Author:
Liam Furness
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