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Silver hexafluorophosphate

Silver hexafluorophosphate, sometimes referred to "silver PF-6," is an inorganic compound with the chemical formula AgPF<sub>6</sub>.

Uses and reactions

Silver hexafluorophosphate is a commonly encountered reagent in inorganic and organometallic chemistry. It is commonly used to replace halide ligands with the weakly coordinating hexafluorophosphate anion; abstraction of the halide is driven by the precipitation of the appropriate silver halide. Illustrative is the preparation of acetonitrile complexes from a metal bromide, a reaction that would typically be conducted in a solution of acetonitrile:

AgPF<sub>6</sub> + Re(CO)<sub>5</sub>Br + CH<sub>3</sub>CN → AgBr + [Re(CO)<sub>5</sub>(CH<sub>3</sub>CN)]PF<sub>6</sub>

Ligands with tightly-bound halide atoms such as xenon difluoride coordinate the silver, but do not themselves decompose:

AgPF<sub>6</sub>&nbsp;+ 2&nbsp;XeF<sub>2</sub>&nbsp;→ [Ag(XeF<sub>2</sub>)<sub>2</sub>]PF<sub>6</sub>.

AgPF<sub>6</sub> can act as an oxidant, forming silver metal as a by-product. For example, in solution in dichloromethane, ferrocene is oxidised to ferrocenium hexafluorophosphate:

AgPF<sub>6</sub> + Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> → Ag + [Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>]PF<sub>6</sub> (E = 0.65 V)

Related reagents

In terms of their properties and applications, silver tetrafluoroborate (AgBF<sub>4</sub>) and the hexafluoroantimonate (AgSbF<sub>6</sub>) are similar to AgPF<sub>6</sub>.

Comparison with silver nitrate

Silver nitrate is a traditional and less expensive halide abstraction reagent, as indicated by its widespread use in qualitative tests for halides.

Relative to AgPF<sub>6</sub>, however, silver nitrate is poorly soluble in weakly basic solvents: the nitrate anion is Lewis basic and presents an interfering ligand that precludes its use in stringent applications.

References