ChemInform Abstract: Disproportionation of Ag(II) to Ag(I) and Ag(III) in Fluoride Systems and Syntheses and Structures of (AgF+) 2AgF4-MF6- Salts (M: As, Sb, Pt, Au, Ru).

Interaction of Ag+ salts in anhydrous liquid hydrogen fluoride, aHF, with AgF4- salts gives amorphous red-brown diamagnetic AgIAgIIIF4, which transforms exothermally to brown, paramagnetic, microcrystalline AgIIF2 below 0 °C. AgIAuIIIF4 prepared from Ag+ and AuF4- in aHF has a tetragonal unit cell and a KBrF4 type lattice, with a = 5.788(1) A, c = 10.806(2) A, and Z = 4. Blue-green AgIIFAsF6 disproportionates in aHF (in the absence of F- acceptors) to colorless AgIAsF6 and a black pseudotrifluoride, (AgIIF+)2AgIIIF4-AsF6-. The latter and other (AgF)2AgF4MF6 salts are also generated by oxidation of AgF2 or AgF+ salts in aHF with F2 or in solutions of O2+MF6- salts (M = As, Sb, Pt, Au, Ru). Single crystals of (AgF)2AgF4AsF6 were grown from an AgFAsF6/AsF5 solution in aHF standing over AgF2 or AgFBF4, with F2 as the oxidant. They are monoclinic, P2/c, at 20 °C, with a = 5.6045(6) A, b = 5.2567(6) A, c = 7.8061(8) A, β = 96.594(9)°, and Z = 1. The structure consists of (AgF)nn+ chains (F−Ag−F = 180°, Ag−F−Ag ...