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Complexes of molybdenum(VI) oxide tetrafluoride and molybdenum(VI) dioxide difluoride with neutral N- and O-donor ligands

Complexes of molybdenum(VI) oxide tetrafluoride and molybdenum(VI) dioxide difluoride with neutral N- and O-donor ligands
Complexes of molybdenum(VI) oxide tetrafluoride and molybdenum(VI) dioxide difluoride with neutral N- and O-donor ligands
[MoOF4(MeCN)], prepared from reaction of MoF6 with (Me3Si)2O in anhydrous MeCN solution, reacts with the neutral O-donor ligands, thf, Ph3PO, Me3PO, dmf and dmso, (L) in a 1:1 molar ratio under rigorously anhydrous conditions to form six-coordinate [MoOF4(L)], which have been characterised by microanalysis, IR, 1H, 19F{1H} and 95Mo NMR spectroscopy. In the presence of moisture the major products are [MoO2F2(L)2], which can be made directly by reaction of [MoOF4(L)] with a further equivalent of L and (Me3Si)2O. [MoOF4(MeCN)] and 2,2′-bipyridyl produce the insoluble [MoOF4(bipy)], which is probably 7-coordinate. Ph3AsO is quantitatively converted to Ph3AsF2 by [MoOF4(MeCN)], and soft ligands, including Me2S, Me3P and Me3As, reduce the oxide fluoride on contact. Unstable [MoO2F2(MeCN)2] has also been prepared and the X-ray structure of [MoO2F2(MeCN)2]·MeCN is reported. X-ray crystal structures are reported for [MoOF4(Ph3PO)], [MoO2F2(Ph3PO)2], [MoO2F2(Me3PO)(H2O)] and [Mo2O4F2(μ-F)2(Me3PO)2]. Comparisons with the corresponding chemistries of WOF4 and WO2F2 are described.
Molybendum, oxide-fluoride, x-ray structures, Nitrogen donor ligand, Oxygen donor ligand
0022-1139
190-197
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Monzittu, Francesco, Matteo
c0124f10-1f2e-47e5-85f4-138fab36b5d4
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Hope, Eric G.
b2554b87-8d1e-4099-947c-0878b04fa5ed
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Monzittu, Francesco, Matteo
c0124f10-1f2e-47e5-85f4-138fab36b5d4
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Hope, Eric G.
b2554b87-8d1e-4099-947c-0878b04fa5ed
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Levason, William, Monzittu, Francesco, Matteo, Reid, Gillian, Hope, Eric G. and Zhang, Wenjian (2017) Complexes of molybdenum(VI) oxide tetrafluoride and molybdenum(VI) dioxide difluoride with neutral N- and O-donor ligands. Journal of Fluorine Chemistry, 200, 190-197. (doi:10.1016/j.jfluchem.2017.06.015). (In Press)

Record type: Article

Abstract

[MoOF4(MeCN)], prepared from reaction of MoF6 with (Me3Si)2O in anhydrous MeCN solution, reacts with the neutral O-donor ligands, thf, Ph3PO, Me3PO, dmf and dmso, (L) in a 1:1 molar ratio under rigorously anhydrous conditions to form six-coordinate [MoOF4(L)], which have been characterised by microanalysis, IR, 1H, 19F{1H} and 95Mo NMR spectroscopy. In the presence of moisture the major products are [MoO2F2(L)2], which can be made directly by reaction of [MoOF4(L)] with a further equivalent of L and (Me3Si)2O. [MoOF4(MeCN)] and 2,2′-bipyridyl produce the insoluble [MoOF4(bipy)], which is probably 7-coordinate. Ph3AsO is quantitatively converted to Ph3AsF2 by [MoOF4(MeCN)], and soft ligands, including Me2S, Me3P and Me3As, reduce the oxide fluoride on contact. Unstable [MoO2F2(MeCN)2] has also been prepared and the X-ray structure of [MoO2F2(MeCN)2]·MeCN is reported. X-ray crystal structures are reported for [MoOF4(Ph3PO)], [MoO2F2(Ph3PO)2], [MoO2F2(Me3PO)(H2O)] and [Mo2O4F2(μ-F)2(Me3PO)2]. Comparisons with the corresponding chemistries of WOF4 and WO2F2 are described.

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Accepted/In Press date: 28 June 2017
Keywords: Molybendum, oxide-fluoride, x-ray structures, Nitrogen donor ligand, Oxygen donor ligand

Identifiers

Local EPrints ID: 412785
URI: http://eprints.soton.ac.uk/id/eprint/412785
ISSN: 0022-1139
PURE UUID: b71ed01f-3e0e-4aa6-b322-c99ce318fd67
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Francesco, Matteo Monzittu: ORCID iD orcid.org/0000-0002-7080-3795
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 01 Aug 2017 16:31
Last modified: 16 Mar 2024 05:34

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Contributors

Author: William Levason ORCID iD
Author: Francesco, Matteo Monzittu ORCID iD
Author: Gillian Reid ORCID iD
Author: Eric G. Hope
Author: Wenjian Zhang

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