Some chemistry of high oxidation state transition metal fluorides in anhydrous HF

Silverland: the Realm of Compounds of Divalent Silver—and Why They are Interesting

“…My quest was finally rewarded, when I came across beautiful papers by Bartlett,Žemva et al [22]. These authors showed that a divalent silver cation is so potent an oxidizer that it may steal an electron from an O 2 molecule; thus, it is capable of doing the same trick as PtF 6 , but at a much lower formal oxidation state of a metal.…”

The Reactions of Silver, Zirconium, and Hafnium Fluorides with Liquid Ammonia: Syntheses and Crystal Structures of Ag(NH3)2F·2NH3, [M(NH3)4F4]·NH3 (M = Zr, Hf), and (N2H7)F

“…Their solution chemistry is quite well known in aqueous solutions, hydrofluoric acid, or anhydrous HF. [1][2][3][4][5] We set out to explore the reactions of fluorides with liquid ammonia, which could yield substances like fluoride ammoniates, amine fluorides and amide-or imide fluorides, [6][7][8][9] or even nitride fluorides and nitrides as the final products of these reactions. [10] With the exception of the nitrides, all these classes of compounds are only scarcely known and could feature interesting properties depending on the metal ion.…”

“…Recently, we reported the reaction of blue-violet Ag 3 M 2 F 14 (M = Zr, Hf) [11,12] with liquid ammonia and established one product to be [Ag(NH 3 ) 3 (µ-NH 3 )Ag(NH 3 ) 4 ]-MF 6 (M = Zr, Hf) featuring Ag-Ag interactions. [6] Now we were able to identify the other products of this complex reaction by X-ray diffraction methods as M(NH 3 ) 4 F 4 ·NH 3 (1, M = Zr; 2, M = Hf) and [NH 4 (NH 3 )]F (3).…”

“…[6] Now we were able to identify the other products of this complex reaction by X-ray diffraction methods as M(NH 3 ) 4 F 4 ·NH 3 (1, M = Zr; 2, M = Hf) and [NH 4 (NH 3 )]F (3). Compounds 1 and 2 can also be obtained from neat MF 4 (M = Zr, Hf) in liquid NH 3 .…”

“…[6] Now we were able to identify the other products of this complex reaction by X-ray diffraction methods as M(NH 3 ) 4 F 4 ·NH 3 (1, M = Zr; 2, M = Hf) and [NH 4 (NH 3 )]F (3). Compounds 1 and 2 can also be obtained from neat MF 4 (M = Zr, Hf) in liquid NH 3 . Mixtures of AgF or AgF 2 /MF 4 (M = Zr, Hf) in liquid ammonia gave the known product [Ag(NH 3 ) 3 -(µ-NH 3 )Ag(NH 3 ) 4 ]MF 6 (M = Zr, Hf), [6] the pentaammoniates M(NH 3 ) 4 F 4 ·NH 3 (1, M = Zr; 2, M = Hf) and Ag(NH 3 ) 2 F· 2NH 3 (4).…”