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Silver(II) fluoride

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Silver(II) fluoride
Silver(II) fluoride
Names
IUPAC name silver(II) fluoride
Other names silver difluoride
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.124 Edit this at Wikidata
EC Number
  • 232-037-5
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/Ag.2FH/h;2*1H/q+2;;/p-2Key: KWVVTSALYXIJSS-UHFFFAOYSA-L
  • InChI=1/Ag.2FH/h;2*1H/q+2;;/p-2Key: KWVVTSALYXIJSS-NUQVWONBAP
SMILES
  • ..
Properties
Chemical formula AgF2
Molar mass 145.865 g/mol
Appearance white or grey crystalline powder, hygroscopic
Density 4.58 g/cm
Melting point 690 °C (1,274 °F; 963 K)
Boiling point 700 °C (1,292 °F; 973 K) (decomposes)
Solubility in water Decomposes
Structure
Crystal structure orthorhombic
Coordination geometry tetragonally elongated
octahedral coordination
Molecular shape linear
Hazards
Occupational safety and health (OHS/OSH):
Main hazards toxic, reacts violently with water, powerful oxidizer
GHS labelling:
Pictograms GHS03: OxidizingGHS05: CorrosiveGHS06: Toxic
Signal word Danger
Hazard statements H272, H301, H302, H311, H312, H314, H331, H332
Precautionary statements P210, P220, P221, P260, P261, P264, P270, P271, P280, P301+P310, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P311, P312, P321, P322, P330, P361, P363, P370+P378, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazard W+OX: Reacts with water in an unusual or dangerous manner AND is oxidizer
3 0 3W
OX
Safety data sheet (SDS) MSDS
Related compounds
Other anions Silver(I,III) oxide
Other cations Copper(II) fluoride
Palladium(II) fluoride
Zinc fluoride
Cadmium(II) fluoride
Mercury(II) fluoride
Related compounds Silver subfluoride
Silver(I) fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

Silver(II) fluoride is a chemical compound with the formula AgF2. It is a rare example of a silver(II) compound - silver usually exists in its +1 oxidation state. It is used as a fluorinating agent.

Preparation

AgF2 can be synthesized by fluorinating Ag2O with elemental fluorine. Also, at 200 °C (473 K) elemental fluorine will react with AgF or AgCl to produce AgF2.

As a strong fluorinating agent, AgF2 should be stored in Teflon or a passivated metal container. It is light sensitive.

AgF2 can be purchased from various suppliers, the demand being less than 100 kg/year. While laboratory experiments find use for AgF2, it is too expensive for large scale industry use. In 1993, AgF2 cost between 1000-1400 US dollars per kg.

Composition and structure

AgF2 is a white crystalline powder, but it is usually black/brown due to impurities. The F/Ag ratio for most samples is < 2, typically approaching 1.75 due to contamination with Ag and oxides and carbon.

For some time, it was doubted that silver was actually in the +2 oxidation state, rather than some combination of states such as Ag, which would be similar to silver(I,III) oxide. Neutron diffraction studies, however, confirmed its description as silver(II). The Ag was found to be present at high temperatures, but it was unstable with respect to AgF2.

In the gas phase, AgF2 is believed to have D∞h symmetry. Crystal structure of AgF2 was determined by single-crystal X-ray diffraction.

Approximately 14 kcal/mol (59 kJ/mol) separate the ground and first excited states. The compound is paramagnetic, but it becomes ferromagnetic at temperatures below −110 °C (163 K).

Uses

AgF2 is a strong fluorinating and oxidising agent. It is formed as an intermediate in the catalysis of gaseous reactions with fluorine by silver. With fluoride ions, it forms complex ions such as AgF
3, the blue-violet AgF
4, and AgF
6.

It is used in the fluorination and preparation of organic perfluorocompounds. This type of reaction can occur in three different ways (here Z refers to any element or group attached to carbon, X is a halogen):

  1. CZ3H + 2 AgF2 → CZ3F + HF + 2 AgF
  2. CZ3X + 2AgF2 → CZ3F + X2 + 2 AgF
  3. Z2C=CZ2 + 2 AgF2 → Z2CFCFZ2 + 2 AgF

Similar transformations can also be effected using other high valence metallic fluorides such as CoF3, MnF3, CeF4, and PbF4.

AgF
2 is also used in the fluorination of aromatic compounds, although selective monofluorinations are more difficult:

C6H6 + 2 AgF2 → C6H5F + 2 AgF + HF

AgF
2 oxidises xenon to xenon difluoride in anhydrous HF solutions.

2 AgF2 + Xe → 2 AgF + XeF2

It also oxidises carbon monoxide to carbonyl fluoride.

2 AgF2 + CO → 2 AgF + COF2

It reacts with water to form oxygen gas:

4 AgF2 + 4 H2O → 2 Ag2O + 8 HF + O2

AgF
2 can be used to selectively fluorinate pyridine at the ortho position under mild conditions.

Safety

AgF
2 is a very strong oxidizer that reacts violently with water, reacts with dilute acids to produce ozone, oxidizes iodide to iodine, and upon contact with acetylene forms the contact explosive silver acetylide. It is light-sensitive, very hygroscopic and corrosive. It decomposes violently on contact with hydrogen peroxide, releasing oxygen gas. It also liberates HF, F
2, and elemental silver.

References

  1. Priest, H. F.; Swinehert, Carl F. (1950). "Anhydrous Metal Fluorides". Inorganic Syntheses. Vol. 3. pp. 171–183. doi:10.1002/9780470132340.ch47. ISBN 978-0-470-13234-0. {{cite book}}: |journal= ignored (help)
  2. Encyclopedia of Chemical Technology. Kirk-Othermer. Vol.11, 4th Ed. (1991)
  3. J.T. Wolan; G.B. Hoflund (1998). "Surface Characterization Study of AgF and AgF2 Powders Using XPS and ISS". Applied Surface Science. 125 (3–4): 251. Bibcode:1998ApSS..125..251W. doi:10.1016/S0169-4332(97)00498-4.
  4. Hans-Christian Miller; Axel Schultz & Magdolna Hargittai (2005). "Structure and Bonding in Silver Halides. A Quantum Chemical Study of the Monomers: Ag2X, AgX, AgX2, and AgX3(X = F, Cl, Br, I)". J. Am. Chem. Soc. 127 (22): 8133–45. doi:10.1021/ja051442j. PMID 15926841.
  5. Jesih, A.; Lutar, K.; Žemva, B.; Bachmann, B.; Becker, St.; Müller, B. G.; Hoppe, R. (1990-01-22). "Einkristalluntersuchungen an AgF 2". Zeitschrift für anorganische und allgemeine Chemie. 588 (1): 77–83. doi:10.1002/zaac.19905880110. ISSN 0044-2313.
  6. Egon Wiberg; Nils Wiberg; Arnold Frederick Holleman (2001). Inorganic chemistry. Academic Press. pp. 1272–1273. ISBN 0-12-352651-5.
  7. Rausch, D.; Davis, r.; Osborne, D. W. (1963). "The Addition of Fluorine to Halogenated Olefins by Means of Metal Fluorides". J. Org. Chem. 28 (2): 494–497. doi:10.1021/jo01037a055.
  8. Zweig, A.; Fischer, R. G.; Lancaster, J. (1980). "New Methods for Selective Monofluorination of Aromatics Using Silver Difluoride". J. Org. Chem. 45 (18): 3597. doi:10.1021/jo01306a011.
  9. Levec, J.; Slivnik, J.; Zemva, B. (1974). "On the Reaction Between Xenon and Fluorine". Journal of Inorganic and Nuclear Chemistry. 36 (5): 997. doi:10.1016/0022-1902(74)80203-4.
  10. Fier, P. S.; Hartwig, J. F. (2013). "Selective C-H Fluorination of Pyridines and Diazines Inspired by a Classic Amination Reaction". Science. 342 (6161): 956–960. Bibcode:2013Sci...342..956F. doi:10.1126/science.1243759. PMID 24264986. S2CID 6584890.
  11. ^ Dale L. Perry; Sidney L. Phillips (1995). Handbook of inorganic compounds. CRC Press. p. 352. ISBN 0-8493-8671-3.
  12. ^ W. L. F. Armarego; Christina Li Lin Chai (2009). Purification of Laboratory Chemicals (6th ed.). Butterworth-Heinemann. p. 490. ISBN 978-1-85617-567-8.
  13. ^ Richard P. Pohanish; Stanley A. Greene (2009). Wiley Guide to Chemical Incompatibilities (3rd ed.). John Wiley and Sons. p. 93. ISBN 978-0-470-38763-4.

External links

Silver compounds
Silver(0,I)
Silver(I)
Organosilver(I) compounds
  • AgC2H3O2
  • AgC22H43O2
  • CH3CH(OH)COOAg
  • C
    18H
    36AgO
    2
  • AgC4H3N2NSO2C6H4NH2
  • AgC
    11H
    23COO
  • Silver(II)
    Silver(III)
    Silver(I,III)
    Salts and covalent derivatives of the fluoride ion
    HF ?HeF2
    LiF BeF2 BF
    BF3
    B2F4
    +BO3
    CF4
    CxFy
    +CO3
    NF3
    FN3
    N2F2
    NF
    N2F4
    NF2
    ?NF5
    OF2
    O2F2
    OF
    O3F2
    O4F2
    ?OF4
    F2 Ne
    NaF MgF2 AlF
    AlF3
    SiF4 P2F4
    PF3
    PF5
    S2F2
    SF2
    S2F4
    SF3
    SF4
    S2F10
    SF6
    +SO4
    ClF
    ClF3
    ClF5
    ?ArF2
    ?ArF4
    KF CaF
    CaF2
    ScF3 TiF2
    TiF3
    TiF4
    VF2
    VF3
    VF4
    VF5
    CrF2
    CrF3
    CrF4
    CrF5
    ?CrF6
    MnF2
    MnF3
    MnF4
    ?MnF5
    FeF2
    FeF3
    FeF4
    CoF2
    CoF3
    CoF4
    NiF2
    NiF3
    NiF4
    CuF
    CuF2
    ?CuF3
    ZnF2 GaF2
    GaF3
    GeF2
    GeF4
    AsF3
    AsF5
    Se2F2
    SeF4
    SeF6
    +SeO3
    BrF
    BrF3
    BrF5
    KrF2
    ?KrF4
    ?KrF6
    RbF SrF
    SrF2
    YF3 ZrF2
    ZrF3
    ZrF4
    NbF4
    NbF5
    MoF4
    MoF5
    MoF6
    TcF4
    TcF
    5

    TcF6
    RuF3
    RuF
    4

    RuF5
    RuF6
    RhF3
    RhF4
    RhF5
    RhF6
    PdF2
    Pd
    PdF4
    ?PdF6
    Ag2F
    AgF
    AgF2
    AgF3
    CdF2 InF
    InF3
    SnF2
    SnF4
    SbF3
    SbF5
    TeF4
    ?Te2F10
    TeF6
    +TeO3
    IF
    IF3
    IF5
    IF7
    +IO3
    XeF2
    XeF4
    XeF6
    ?XeF8
    CsF BaF2   LuF3 HfF4 TaF5 WF4
    WF5
    WF6
    ReF4
    ReF5
    ReF6
    ReF7
    OsF4
    OsF5
    OsF6
    ?OsF
    7

    ?OsF
    8
    IrF2
    IrF3
    IrF4
    IrF5
    IrF6
    PtF2
    Pt
    PtF4
    PtF5
    PtF6
    AuF
    AuF3
    Au2F10
    ?AuF6
    AuF5•F2
    Hg2F2
    HgF2
    ?HgF4
    TlF
    TlF3
    PbF2
    PbF4
    BiF3
    BiF5
    ?PoF2
    PoF4
    PoF6
    AtF
    ?AtF3
    ?AtF5
    RnF2
    ?RnF
    4

    ?RnF
    6
    FrF RaF2   LrF3 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
    LaF3 CeF3
    CeF4
    PrF3
    PrF4
    NdF2
    NdF3
    NdF4
    PmF3 SmF
    SmF2
    SmF3
    EuF2
    EuF3
    GdF3 TbF3
    TbF4
    DyF2
    DyF3
    DyF4
    HoF3 ErF3 TmF2
    TmF3
    YbF2
    YbF3
    AcF3 ThF3
    ThF4
    PaF4
    PaF5
    UF3
    UF4
    UF5
    UF6
    NpF3
    NpF4
    NpF5
    NpF6
    PuF3
    PuF4
    PuF5
    PuF6
    AmF2
    AmF3
    AmF4
    ?AmF6
    CmF3
    CmF4
     ?CmF6
    BkF3
    BkF
    4
    CfF3
    CfF4
    EsF3
    EsF4
    ?EsF6
    Fm Md No
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