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Molybdenum difluoride dioxide

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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).
Chemical compound

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

Structure

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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

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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

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  • 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

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  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. ^ a b 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.
Salts and covalent derivatives of the fluoride ion
HF ?HeF2
FrF RaF2   LrF3 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
PF6, AsF6, SbF6 compounds
AlF2−5, AlF3−6 compounds
chlorides, bromides, iodides
and pseudohalogenides
SiF2−6, GeF2−6 compounds
Oxyfluorides
Organofluorides
with transition metal,
lanthanide, actinide, ammonium
nitric acids
bifluorides
thionyl, phosphoryl,
and iodosyl

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