Ag3L4 (L= SO3F, SbF6) and Ag9(PO2F2)14 – rare

examples of mixed-valence salts of Ag(I)/Ag(II) 1,2

Tomasz Michałowskia, Zoran Mazejb, Evgeny Goreshnik,b Zvonko Jagličićc, Iztok Arčon,d,e Przemysław Malinowski,f
Mariana Derzsi,f Jadwiga Szydłowska,a and Wojciech Grochalaf
a Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
b Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
c University of Ljubljana, Faculty of Civil and Geodetic Engineering and Institute of Mathematics, Physics and Mechanics, Jadranska 19, SI-1000 Ljubljana, Slovenia
d University of Nova Gorica, SI–5000 Nova Gorica, Slovenia
e Department of Low and Medium Energy Physics, Jožef Stefan Institute, SI–1000 Ljubljana, Slovenia
f CENT, University of Warsaw, Żwirki i Wigury 93, 02-089 Warsaw, Poland

Superacids
Theory Pros Cons HSO3F HSbF6 HPO2F2
• Acidity greater than 100% pure H2SO4 • applications in organic and • highly corrosive nature CAS 7789-21-2 16950-06-4 13779-41-4
inorganic synthesis :
• pH only for diluted solutions Density 1.84 g/cm3 2.885 g/cm3 1.583 g/cm3
➢ source of weakly • high Brønsted and Lewis
• Henderson-Hasselbalch equation invalid coordinating anions acidity mp -87oC no data -96.5°C
• pH of aqueous solutions changed to a ➢ fluorinating agents
Hammett acidity function: ➢ catalysts • controlled, moisture-free bp 165oC decomposes 115.9°C
➢ usually support action of environment necessary H0 –15.1 –31.3 –8.9
H0 = pKBH+ + log[B]/[BH+] strong oxidizers (such as
Ag(II)) • reaction vessels WoS
• stabilization of high made of chemically hits for 248 440 53
H0 (100% pure H2SO4) = –12 oxidation states resistant materials salts

Syntheses
3 AgSO3F + BrSO3F 2 AgSbF6 + Ag(SbF6)2 9 AgF2 + 16 HPO2F2
= = (aHF) = =
1
Ag3(SO3F)4 + /2Br2 Ag3(SbF6)4 Ag9(PO2F2)14 + 18 PO3F + O2

Crystal structures

Structure of Ag3(SO3F)43,4 Structure of Ag3(SbF6)45 Structure of Ag9(PO2F2)146

localized valence Ag(II)/Ag(I) disorder localized valence
Compound System Space group a /Å b /Å c /Å α /o β /o γ /o V/Å3

Ag3(SO3F)4 monoclinic P21/c 5.337 12.948 19.597 90 100.639 90 1330.95

Ag3(SbF6)4 cubic I–43d 12.378 12.378 12.378 90 90 90 1896.49

Ag9(PO2F2)14 monoclinic P21/c 9.907 10.188 24.147 90 105.114 90 2352.91

All salts in question are of mixed–valence character (insulators). Quest for metallic intermediate valence systems 7,8 continues.

Selected literature
1. Wang Q. –M., et al., New J. Chem. (2002) 26, 513. 4. Michałowski T, et al., Eur. J. Inorg. Chem. (2011), 16, 2508. 7. Grochala W., Hoffman R., Angew. Chem. Int. Ed. Engl. (2001)
2. Bartlett N., personal communication to W. Grochala (2001). 5. Mazej Z., et al., manuscript in preparation (2014). 40, 2742.
3. Leung P. C., Aubke F. Inorg. Chem. (1978) 17, 1765. 6. Malinowski P., Grochala W., manuscript in preparation (2014). 8. Grochala W., J. Mater. Chem. (2009) 19, 6949.