Molybdenum difluoride dioxide

Molybdenum difluoride dioxide is the inorganic compound with the formula MoF2O2. It is a white, diamagnetic, volatile solid.[1]

Molybdenum difluoride dioxide
Names
Other names
molybdenum dioxide difluoride
Identifiers
3D model (JSmol)
  • InChI=1S/2FH.Mo.2O/h2*1H;;;/q;;+2;;/p-2
    Key: RMUNMMZEBAMTER-UHFFFAOYSA-L
  • O=[Mo](F)(F)=O
Properties
F2MoO2
Molar mass 165.94 g·mol−1
Appearance white solid
Density 3.82 g/cm3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Structure
Structure of solid MoF2O2. X positions are occupied by O or F.

Gaseous molybdenum difluoride dioxide is a tetrahedral molecule.[2] According to X-ray crystallography, the solid is a coordination polymer consisting of trigonal primatic chains of made by linking Mo3F6O6 monomers. The fluoride and oxide positions are disordered.[3] 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:[3]

Na2MoO4 + 4 HF → Na2MoF4O2 + 2 H2O

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

Na2MoF4O2 → 2 NaF + MoF2O2

The compound also arises by hydrolysis of molybdenum oxytetrafluoride:

MoF4O + H2O → 2 HF + MoF2O2

The compound dissolves in dimethylformamide to give a bis(adduct):[4]

MoF2O2 + 2 OC(H)N(CH3)2 → MoF2O2(OC(H)N(CH3)2)2

Further reading
  • Edwards, A. J.; Steventon, B. R. (1968). "Fluoride crystal structures. Part II. Molybdenum oxide tetrafluoride". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 2503. doi:10.1039/j19680002503.
  • Turnbull, Douglas; Chaudhary, Praveen; Leenstra, Dakota; Hazendonk, Paul; Wetmore, Stacey D.; Gerken, Michael (2020). "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)". Inorganic Chemistry. 59 (23): 17544–17554. doi:10.1021/acs.inorgchem.0c02783. PMID 33200611. S2CID 226989898.

References
  1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 1023. ISBN 978-0-08-037941-8.
  2. Ward, Brian G.; Stafford, Fred E. (1968). "Synthesis and Structure of Four- and Five-Coordinated Gaseous Oxohalides of Molybdenum(VI) and Tungsten(VI)". Inorganic Chemistry. 7 (12): 2569–2573. doi:10.1021/ic50070a020.
  3. Shorafa, Hashem; Ficicioglu, Halil; Tamadon, Farhad; Girgsdies, Frank; Seppelt, Konrad (2010). "Molybdenum Difluoride Dioxide, MoO2F2". Inorganic Chemistry. 49 (9): 4263–4267. doi:10.1021/ic1000864. PMID 20380384.
  4. Benjamin, Sophie L.; Levason, William; Reid, Gillian (2013). "Medium and high oxidation state metal/Non-metal fluoride and oxide–fluoride complexes with neutral donor ligands". Chem. Soc. Rev. 42 (4): 1460–1499. doi:10.1039/C2CS35263J. PMID 23014811.
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