Fluorosulfates

The fluorosulfates or fluorosulfonates are a set of salts of fluorosulfuric acid with an ion formula SO3F−. The flurosulfate anion can be teated as though it was a hydrogen sulfate anion with hydroxyl substituted with fluorine.[1] The fluorosulfate ion has a low propensity for form complexes with the metal cation. Since fluorine is similar in size to oxygen the fluorosulfate ion is roughly tetrahedral and forms salts similar to those of perchlorate. When an organic group is substituted for the anions, organic fluorosulfonates are formed.

In solution the fluorosulfate anion is completely ionised. The volume is 47.8 cm3/mol.[2] Nearly every metal ion and quaternary ammonium ions can form a salt with flourosulfate.[2] Different ways to make these salts include treating a metal chloride with anhydrous fluorosulfuric acid which releases hydrogen chloride gas. Double decomposition methods with a metal sulfate with barium fluorosulfate, or a metal chloride with silver fluorosulfate, leave the metal salt in solution.[2]

Related ionic compounds are the fluoroselenites SeO3F− and the fluorosulfites SO2F−.[3]

Compounds

formula name colour decomposition temp decomposition product crystal ref
LiSO3F Lithium fluorosulfate C2/m a=8.54 b=7.62 c=4.98 β=90.0 V=81 [1]
NaSO3F sodium fluorosulfate Hexagonal a=5.4812 b=5.4812 c=6.5172 V=169.57 Z=2 D=2.390 [1]
KSO3F potassium fluorosulfate Pnma a=8.62 b=5.84 c=7.35 V=92.5 [1]
RbSO3F Rubidium fluorosulfate Orthorhombic Pnma a=8.7812 b=6.0318 c=7.5108 V=397.82 Z=4 D=3.081 [1]
CsSO3F caesium fluorosulfate l41/a a=5.611 b=5.611 c=14.13 V=111.3 Z=4 [1]
TlSO3F thallium fluorosulfate Orthorhombic a=5.2205 b=5.5141 c=13.4378 V=386.83 Z=4 D=5.210 [1]
NH4SO3F ammonium fluorosulfate Orthorhombic Pnma a=8.97 b=6.00 c=7.54 V=101.4 Z=4 [1]
N(CH3)4SO3F tetramethyl ammonium fluorosulfate Orthorhombic Pnma a=8.38 b=8.38 c=5.86 V=102.88 Z=4 [1]
CrO2(SO3F)2 chromyl fluorosulfate green or brown [4]
Fe(III)(SO3F)3 ferric fluorosulfate green grey 230 S2O5F2 SO3 FeF3 [5]
Cu(II)(SO3F)2 cupric fluorosulfate pale yellow/white 210 S2O5F2 SO3 CuSO4 CuF2 [5]
Zn(II)(SO3F)2 zinc fluorosulfate white 280 SO3 ZnF2 [5]
Ag(I)SO3F silver fluorosulfate P21/m a=5.413 b=8.174 c=7.544 β=94.60 V=83.17 Z=4 [1]
Ag(II)(SO3F)2 silver(II) fluorosulfate dark brown room temperature fast >120 Ag3(SO3F)4 SO3F• monoclinic a=10.5130 Å, b= 7.7524 Å, c = 8.9366 Å, β = 117.867(2)° V =643.88(5) Å3, Z = 4, d. = 3.15 gcm–3] [6]
Ag3(SO3F)4 black [6]
Au(II)(SO3F)2 yellow red [7]
Au(III)(SO3F)2 [7]
Si(SO3F)4 silicon tetraflourosulfonate S2O5F2 [3]
Sn(SO3F)4 tin tetraflourosulfonate S2O5F2 [3]
Ti(SO3F)4 titanium tetraflourosulfonate S2O5F2 [3]
As(SO3F)3 arsenic triflourosulfonate S2O5F2 [3]
PO(SO3F)3 phosphoryl triflourosulfonate S2O5F2 [3]
Mg(SO3F)2 magnesium flourosulfonate [3]
NOSO3F nitrosyl fluorosulfonate melts 156° [3]
IF3(SO3F)2 [3]
Nb(SO3F)5 niobium pentafluorosulfonate colourless solution 25 SO3 [8]
Ta(SO3F)5 tantalum pentafluorosulfonate
pentakis(fluorosulfato)tantalum(V)		 colourless solution [8]

References

  1. 1 2 3 4 5 6 7 8 9 10 Michałowski, Tomasz; Leszczyński, Piotr J.; Cyrański, Michał; Dobrzycki, Łukasz; Budzianowski, Armand; Grochala, Wojciech (August 2012). "The missing crystal structures of fluorosulfates of monovalent cations: M(I)SO3F, M=Na, Rb and Tl". Journal of Fluorine Chemistry. 140: 116–120. doi:10.1016/j.jfluchem.2012.05.004.
  2. 1 2 3 Lawrance, Geoffrey A. (February 1986). "Coordinated trifluoromethanesulfonate and fluorosulfate". Chemical Reviews. 86 (1): 17–33. doi:10.1021/cr00071a002.
  3. 1 2 3 4 5 6 7 8 9 Simons, J. H. (1964). Fluorine Chemistry volume 5. Elsevier. pp. 71–72. ISBN 9780323147248.
  4. ↑ Ben Altabef, A.; Brandán, S.A. (September 2010). "A new vibrational study of chromyl fluorosulfate, CrO2(SO3F)2 by DFT calculations". Journal of Molecular Structure. 981 (1-3): 146–152. doi:10.1016/j.molstruc.2010.07.045.
  5. 1 2 3 Goubeau, J.; Milne, J. B. (15 October 1967). "Preparation and characterization of Zn(II), Cu(II), and Fe(III) fluorosulfates". Canadian Journal of Chemistry. 45 (20): 2321–2326. doi:10.1139/v67-378.
  6. 1 2 Malinowski, Przemysław J.; Derzsi, Mariana; Mazej, Zoran; Jagličić, Zvonko; Leszczyński, Piotr J.; Michałowski, Tomasz; Grochala, Wojciech (June 2011). "Silver(II) Fluorosulfate: A Thermally Fragile Ferromagnetic Derivative of Divalent Silver in an Oxa-Ligand Environment". European Journal of Inorganic Chemistry. 2011 (16): 2499–2507. doi:10.1002/ejic.201100077.
  7. 1 2 Willner, H.; Mistry, F.; Hwang, G.; Herring, F.G.; Cader, M.S.R.; Aubke, F. (April 1991). "Fluorosulfate derivatives of divalent gold". Journal of Fluorine Chemistry. 52 (1): 13–27. doi:10.1016/S0022-1139(00)80318-8.
  8. 1 2 Cicha, Walter Vladimir (1984). Fluorosulfate Derivatives of Niobium and Tanatalum and their behavior as Components of Novel Super Acid Systems (Thesis). University of British Columbia. pp. 107,138.
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