Silver(III) fluoride explained

Silver(III) fluoride, AgF3, is an unstable, bright-red, diamagnetic compound containing silver in the unusual +3 oxidation state. Its crystal structure is very similar to that of gold(III) fluoride: it is a polymer consisting of rectangular AgF4 units linked into chains by fluoro bridges.[1]

Preparation

AgF3 can be prepared by treating a solution containing tetrafluoroargentate(III) ions in anhydrous hydrogen fluoride with boron trifluoride;[2] the potassium tetrafluoroargentate(III) was prepared by heating a stoichiometric mix of potassium and silver nitrate in a sealed container filled with pressurised fluorine gas at 400C for 24 hours, twice. When dissolved in anhydrous HF, it decomposes spontaneously to Ag3F8 overnight at room temperature. The high-valence silver compounds described in the thesis are notable for their variety of colours: KAgF4 is bright orange, AgF3 bright red, AgFAsF6 is deep blue, Ag3F8 deep red-brown, and Pd(AgF4)2 is lime-green.

Earlier preparations used krypton difluoride as fluorinating agent, and tended to produce the mixed-valence Ag3F8 which may be thought of as silver(II) tetrafluoroargentate(III); Ag2F5, which is (AgF)+AgF4, is formed by reacting AgF3 with AgFAsF6.

References

  1. Silver Trifluoride: Preparation, Crystal Structure, Some Properties, and Comparison with AuF3 . J Am Chem Soc . 1991 . 113 . 4192–4198 . 10.1021/ja00011a021. Zemva . Boris . Lutar . Karel . Jesih . Adolf . Casteel . William J. . Wilkinson . Angus P. . Cox . David E. . von Dreele . Robert B. . Borrmann . Horst . Bartlett . Neil . 11 .
  2. PhD . Casteel . William . September 1992 . The Synthesis and Structural Characterization of Novel Transition Metal Fluorides .