The University of Southampton
University of Southampton Institutional Repository

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.

Text
1-s2.0-S0022113917301495-main - Accepted Manuscript
Download (906kB)
Text
1-s2.0-S0022113917301495-main - Version of Record
Available under License Creative Commons Attribution.
Download (853kB)

More information

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

Catalogue record

Date deposited: 01 Aug 2017 16:31
Last modified: 08 Oct 2020 04:37

Export record

Altmetrics

Contributors

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

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×