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

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posted on 2017-08-25, 13:30 authored by William Levason, Francesco M. Monzittu, Gillian Reid, Wenjian Zhang, Eric G. Hope
[MoOF 4 (MeCN)], prepared from reaction of MoF 6 with (Me 3 Si) 2 O in anhydrous MeCN solution, reacts with the neutral O-donor ligands, thf, Ph 3 PO, Me 3 PO, dmf and dmso, (L) in a 1:1 molar ratio under rigorously anhydrous conditions to form six-coordinate [MoOF 4 (L)], which have been characterised by microanalysis, IR, 1 H, 19 F{ 1 H} and 95 Mo NMR spectroscopy. In the presence of moisture the major products are [MoO 2 F 2 (L) 2 ], which can be made directly by reaction of [MoOF 4 (L)] with a further equivalent of L and (Me 3 Si) 2 O. [MoOF 4 (MeCN)] and 2,2′-bipyridyl produce the insoluble [MoOF 4 (bipy)], which is probably 7-coordinate. Ph 3 AsO is quantitatively converted to Ph 3 AsF 2 by [MoOF 4 (MeCN)], and soft ligands, including Me 2 S, Me 3 P and Me 3 As, reduce the oxide fluoride on contact. Unstable [MoO 2 F 2 (MeCN) 2 ] has also been prepared and the X-ray structure of [MoO 2 F 2 (MeCN) 2 ]·MeCN is reported. X-ray crystal structures are reported for [MoOF 4 (Ph 3 PO)], [MoO 2 F 2 (Ph 3 PO) 2 ], [MoO 2 F 2 (Me 3 PO)(H 2 O)] and [Mo 2 O 4 F 2 (μ-F) 2 (Me 3 PO) 2 ]. Comparisons with the corresponding chemistries of WOF 4 and WO 2 F 2 are described.

Funding

We thank EPSRC for support (EP/K039466, EP/M023664, and EP/N035437/1). FMM thanks the EPSRC and GE Healthcare for a Case studentship.

History

Citation

Journal of Fluorine Chemistry, 2017, 200, pp. 190-197

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

  • VoR (Version of Record)

Published in

Journal of Fluorine Chemistry

Publisher

Elsevier

issn

0022-1139

Acceptance date

2017-06-28

Copyright date

2017

Available date

2017-08-25

Publisher version

http://www.sciencedirect.com/science/article/pii/S0022113917301495

Notes

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jfluchem.2017.06.015.

Language

en

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