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Phosphine and diphosphine complexes of tungsten(VI) oxide tetrafluoride

Phosphine and diphosphine complexes of tungsten(VI) oxide tetrafluoride
Phosphine and diphosphine complexes of tungsten(VI) oxide tetrafluoride
The reaction of [WOF4(MeCN)] with the diphosphines, Me2PCH2CH2PMe2 or o-C6H4(PMe2)2, in anhydrous Et2O produced high yields of [WOF4(diphosphine)], the X-ray crystal structures of which reveal seven-coordinate pentagonal bipyramidal molecules with axial O/F. In contrast, the reaction of [WOF4(MeCN)] and PMe3 forms the six-coordinate [WOF4(PMe3)]. These unusual W(VI) complexes have been characterised by microanalysis, IR, 1H, 19F{1H} and 31P{1H} NMR spectroscopy. The second-order 19F{1H} and 31P{1H} NMR spectra of the [WOF4(diphosphine)] have been analysed. Similar complexes do not form with the other o-phenylene-linked bidentate ligands, o-C6H4(PPh2)2, o-C6H4(AsMe2)2 or o-C6H4(SMe)2.
tungsten, oxide-fluoride, phosphine, diphosphine, x-ray structures, 19F and 31P NMR
0022-1139
74-79
Emsley, James W.
9d219d5e-28c0-4a8c-bf3d-1f78cd707c17
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
De Luca, Giuseppina
8152f554-4aa6-42bf-af23-c0d74db9f69e
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Emsley, James W.
9d219d5e-28c0-4a8c-bf3d-1f78cd707c17
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
De Luca, Giuseppina
8152f554-4aa6-42bf-af23-c0d74db9f69e
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Emsley, James W., Levason, William, Reid, Gillian, De Luca, Giuseppina and Zhang, Wenjian (2017) Phosphine and diphosphine complexes of tungsten(VI) oxide tetrafluoride. Journal of Fluorine Chemistry, 197, 74-79. (doi:10.1016/j.jfluchem.2017.02.007).

Record type: Article

Abstract

The reaction of [WOF4(MeCN)] with the diphosphines, Me2PCH2CH2PMe2 or o-C6H4(PMe2)2, in anhydrous Et2O produced high yields of [WOF4(diphosphine)], the X-ray crystal structures of which reveal seven-coordinate pentagonal bipyramidal molecules with axial O/F. In contrast, the reaction of [WOF4(MeCN)] and PMe3 forms the six-coordinate [WOF4(PMe3)]. These unusual W(VI) complexes have been characterised by microanalysis, IR, 1H, 19F{1H} and 31P{1H} NMR spectroscopy. The second-order 19F{1H} and 31P{1H} NMR spectra of the [WOF4(diphosphine)] have been analysed. Similar complexes do not form with the other o-phenylene-linked bidentate ligands, o-C6H4(PPh2)2, o-C6H4(AsMe2)2 or o-C6H4(SMe)2.

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Accepted/In Press date: 25 February 2017
e-pub ahead of print date: 20 March 2017
Published date: May 2017
Keywords: tungsten, oxide-fluoride, phosphine, diphosphine, x-ray structures, 19F and 31P NMR
Organisations: Chemistry, FIMS

Identifiers

Local EPrints ID: 407595
URI: https://eprints.soton.ac.uk/id/eprint/407595
ISSN: 0022-1139
PURE UUID: c8516910-e518-43e0-82b6-61fd5e965fa9
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 16 Apr 2017 16:59
Last modified: 17 Sep 2019 01:11

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