Molybdenum difluoride dioxide explained

Molybdenum difluoride dioxide is the inorganic compound with the formula MoF₂O₂. It is a white, diamagnetic, volatile solid.

Structure

Gaseous molybdenum difluoride dioxide is a tetrahedral molecule.^[1] According to X-ray crystallography, the solid is a coordination polymer consisting of trigonal primatic chains of made by linking monomers. The fluoride and oxide positions are disordered.^[2] A similar motif is adopted by titanium tetrafluoride.

Synthesis and reactions

The compound can be obtained by thermal decomposition of the dioxotetrafluoride, which in turn is obtained from sodium molybdate:^[2]

Heating sodium dioxotetrafluoride to 400 °C gives monomeric difluoride dioxide, which polymerizes upon condensation:

The compound also arises by hydrolysis of molybdenum oxytetrafluoride:

The compound dissolves in dimethylformamide to give a bis(adduct):^[3]

Further reading

• 10.1039/j19680002503 . Fluoride crystal structures. Part II. Molybdenum oxide tetrafluoride . 1968 . Edwards . A. J. . Steventon . B. R. . Journal of the Chemical Society A: Inorganic, Physical, Theoretical . 2503 .
• 10.1021/acs.inorgchem.0c02783 . Reactions of Molybdenum and Tungsten Oxide Tetrafluoride with Sulfur(IV) Lewis Bases: Structure and Bonding in [WOF4]4, MOF4(OSO), and [SF3][M2O2F9] (M = Mo, W) . 2020 . Turnbull . Douglas . Chaudhary . Praveen . Leenstra . Dakota . Hazendonk . Paul . Wetmore . Stacey D. . Gerken . Michael . Inorganic Chemistry . 59 . 23 . 17544–17554 . 33200611 . 226989898 .

References

1. 10.1021/ic50070a020 . Synthesis and Structure of Four- and Five-Coordinated Gaseous Oxohalides of Molybdenum(VI) and Tungsten(VI) . 1968 . Ward . Brian G. . Stafford . Fred E. . Inorganic Chemistry . 7 . 12 . 2569–2573 .
2. 10.1021/ic1000864 . Molybdenum Difluoride Dioxide, MoO2F2 . 2010 . Shorafa . Hashem . Ficicioglu . Halil . Tamadon . Farhad . Girgsdies . Frank . Seppelt . Konrad . Inorganic Chemistry . 49 . 9 . 4263–4267 . 20380384 .
3. 10.1039/C2CS35263J . Medium and high oxidation state metal/Non-metal fluoride and oxide–fluoride complexes with neutral donor ligands . 2013 . Benjamin . Sophie L. . Levason . William . Reid . Gillian . Chem. Soc. Rev. . 42 . 4 . 1460–1499 . 23014811 .