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Silver(II) fluoride

Silver(II) fluoride is a chemical compound with the formula AgF<sub>2</sub>. 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.

Composition and structure

AgF<sub>2</sub> 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<sup>I</sup>[Ag<sup>III</sup>F<sub>4</sub>], which would be similar to silver(I,III) oxide. Neutron diffraction studies, however, confirmed its description as silver(II). The Ag<sup>I</sup>[Ag<sup>III</sup>F<sub>4</sub>] was found to be present at high temperatures, but it was unstable with respect to AgF<sub>2</sub>.

In the gas phase, AgF<sub>2</sub> is believed to have D<sub>∞h</sub> symmetry. Per single-crystal X-ray diffraction, the silver atoms are square planar-coordinated in the solid state.

Approximately 14 kcal/mol (59 kJ/mol; 0.61&nbsp;eV/f.u.) separate the ground and first excited states. The compound is paramagnetic, but it becomes ferromagnetic at temperatures below −110&nbsp;°C (163 K).

Preparation

AgF<sub>2</sub> can be synthesized by fluorinating Ag<sub>2</sub>O with elemental fluorine. Also, at 200&nbsp;°C (473 K) elemental fluorine will react with AgF or AgCl to produce AgF<sub>2</sub>.

Uses

AgF<sub>2</sub> 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 , the blue-violet , and .

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. CZ<sub>3</sub>H + 2 AgF<sub>2</sub> → CZ<sub>3</sub>F + HF + 2 AgF
  2. CZ<sub>3</sub>X + 2AgF<sub>2</sub> → CZ<sub>3</sub>F + X<sub>2</sub> + 2 AgF
  3. Z<sub>2</sub>C=CZ<sub>2</sub> + 2 AgF<sub>2</sub> → Z<sub>2</sub>CFCFZ<sub>2</sub> + 2 AgF

Similar transformations can also be effected using other high valence metallic fluorides such as CoF<sub>3</sub>, MnF<sub>3</sub>, CeF<sub>4</sub>, and PbF<sub>4</sub>.

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

C<sub>6</sub>H<sub>6</sub> + 2 AgF<sub>2</sub> → C<sub>6</sub>H<sub>5</sub>F + 2 AgF + HF

oxidises xenon to xenon difluoride in anhydrous HF solutions.

2 AgF<sub>2</sub> + Xe → 2 AgF + XeF<sub>2</sub>

It also oxidises carbon monoxide to carbonyl fluoride.

2 AgF<sub>2</sub> + CO → 2 AgF + COF<sub>2</sub>

It reacts with water to form oxygen gas:

4 AgF<sub>2</sub> + 4 H<sub>2</sub>O → 2 Ag<sub>2</sub>O + 8 HF + O<sub>2</sub>

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

Safety

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, , and elemental silver.

References

External links