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 were a hydrogen sulfate anion with hydroxyl substituted by fluorine.[1] The fluorosulfate ion has a low propensity to 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. It is isoelectronic with hydrogen sulfate, HSO4−.[2] 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.[3] Nearly every metal ion and quaternary ammonium ions can form a salt with flourosulfate.[3] 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.[3]

The fluorosulfate anion is weakly coordinating, and is difficult to oxidise. It is important historically as a model weakly coordinating anion. But in the twenty-first century fluorosulfate was superseded in this use, in particular by BARF.[2]

Many pseudobinary fluorosulfate salts are known. They are called pseudobinary, because although there is one other element, there are four kinds of atoms. Non-metal pseudobinary fluorosulfates are known including those of halogens and xenon.[2]

Some psudoternary fluorosulfates exist including Cs[Sb(SO3F)6], Cs[Au(SO3F)4], Cs2[Pt(SO3F)6][2]

Related ionic compounds are the fluoroselenites SeO3F− and the fluorosulfites SO2F−.[4]

Compounds

Formula Name Colour Decomposition temperature /°C Decomposition product Crystal Ref
S2O6F2 bis(fluorosulfuryl) peroxide [2]
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]
TlIII(SO3F)3 thallium tri(fluorosulfate)
thallium(III) fluorosulfonate		 [5]
NH4SO3F ammonium fluorosulfate Orthorhombic Pnma a=8.97 b=6.00 c=7.54 V=101.4 Z=4 [1]
N(CH3)4SO3F tetramethylammonium fluorosulfate Orthorhombic Pnma a=8.38 b=8.38 c=5.86 V=102.88 Z=4 [1]
CrVIO2(SO3F)2 chromyl fluorosulfate green or brown [6]
FeIII(SO3F)3 ferric fluorosulfate green grey 230 S2O5F2
SO3
FeF3		 [7]
CuII(SO3F)2 cupric fluorosulfate
copper(II) fluorosulfate		 pale yellow/white 210 S2O5F2
SO3
CuSO4
CuF2		 [7]
Zn(SO3F)2 zinc fluorosulfate white 280 SO3
ZnF2		 [7]
AgISO3F silver fluorosulfate P21/m a=5.413 b=8.174 c=7.544 β=94.60 V=83.17 Z=4 [1]
AgII(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] [8]
AgI2AgII(SO3F)4 silver(I, II) fluorosulfate black [8]
AuII(SO3F)2 gold(II) fluorosulfate yellow red [9]
Si(SO3F)4 silicon tetraflourosulfonate S2O5F2
SiO2		 [4]
SnIV(SO3F)4 tin tetraflourosulfonate
tin(IV) fluorosulfonate		 S2O5F2 [4]
TiIV(SO3F)4 titanium tetraflourosulfonate
titanium(IV) fluorosulfonate		 S2O5F2 [4]
AsIII(SO3F)3 arsenic triflourosulfonate
arsenic(III) fluorosulfonate		 S2O5F2 [4]
PVO(SO3F)3 phosphoryl triflourosulfonate S2O5F2 [4]
Mg(SO3F)2 magnesium flourosulfonate [4]
Al(SO3F)3 aluminium fluorosulfate white polymeric, fluorosulfate is bidentate and bridged [10]
GaIII(SO3F)3 gallium fluorosulfate white polymeric [11]
InIII(SO3F)3 Indium tri(fluorosulfate) polymeric [5]
NIIIOSO3F nitrosyl fluorosulfonate melts 156 [4]
ClSO3F chlorosulfuryl fluoride [2]
BrSO3F bromosulfuryl fluoride red liquid [2]
IVF3(SO3F)2 [4]
XeII(SO3F)2 xenon(II) fluorosulfate [2]
NbV(SO3F)5 niobium pentafluorosulfonate
niobium(V) fluorosulfate		 colourless solution 25 SO3 [12]
TaV(SO3F)5 tantalum pentafluorosulfonate
pentakis(fluorosulfonato)tantalum(V)		 colourless solution [12]
PbIV(SO3F)4 lead(IV) fluorosulfate [12][13]
BiIII(SO3F)3 bismuth(III) fluorosulfate
tris(fluorosulfonato)bismuth(III)		 [12][14]
ThIV(SO3F)4 thorium(IV) fluorosulfate [12]
UIV(SO3F)4 uranium(IV) fluorosulfate [12][15]
UIVO(SO3F)2 oxouranium(IV) fluorosulfate [15]
UVIO2(SO3F)2 uranyl fluorosulfate
dioxouranium(VI) fluorosulfate		 [15]

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 4 5 6 7 8 Michałowski, Tomasz; Malinowski, Przemysław J.; Grochala, Wojciech (September 2016). "Synthesis, crystal structures, and selected properties of metal fluorosulfates(VI)". Journal of Fluorine Chemistry. 189: 102–118. doi:10.1016/j.jfluchem.2016.07.024.
  3. 1 2 3 Lawrance, Geoffrey A. (February 1986). "Coordinated trifluoromethanesulfonate and fluorosulfate". Chemical Reviews. 86 (1): 17–33. doi:10.1021/cr00071a002.
  4. 1 2 3 4 5 6 7 8 9 Simons, J. H. (1964). Fluorine Chemistry volume 5. Elsevier. pp. 71–72. ISBN 9780323147248.
  5. 1 2 Paul, R. C., Sharma, R. D., Singh, S., & Verma, R. D. (1981). "Indium and thalium fluorosulphates". Journal of Inorganic and Nuclear Chemistry. 43 (8): 1919–1920.
  6. ↑ 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. Bibcode:2010JMoSt.981..146B. doi:10.1016/j.molstruc.2010.07.045.
  7. 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.
  8. 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.
  9. ↑ 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.
  10. ↑ Singh, Sukhjinder; Verma, Rajendar D. (January 1983). "Aluminium tris(flourosulphate)". Polyhedron. 2 (11): 1209–1210. doi:10.1016/S0277-5387(00)84360-0.
  11. ↑ Storr, A.; Yeats, P. A.; Aubke, F. (February 1972). "Gallium(III)-trisfluorosulfate". Canadian Journal of Chemistry. 50 (3): 452–454. doi:10.1139/v72-068.
  12. 1 2 3 4 5 6 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.
  13. ↑ Carter, Henry A., Charles A. Milne, and F. Aubke (1975). "Lead (IV) fluorosulphate". Journal of Inorganic and Nuclear Chemistry. 37 (1): 282–283.(not consulted)
  14. ↑ Paul, R. C.; Singh, S.; Kumar, R. C.; Sharma, R. D.; Verma, R. D. (1979). "NATURE OF TRIS (FLUOROSULPHATO) BISMUTH (III) AND CHLOROBIS (FLUOROSULPHATO) BISMUTH (III)". Indian Journal of Chemistry Section A-Inorganic Bio-Inorganic Physical Theoretical & Analytical Chemistry. 17 (3): 273–275.(not consulted)
  15. 1 2 3 Paul, R.C.; Singh, Sukhijinder; Verma, Rajendar D. (August 1980). "Dioxouranium(VI) and oxouranium(IV) fluorosulphates and double fluorosulphates of uranium(IV)". Journal of Fluorine Chemistry. 16 (2): 153–160. doi:10.1016/S0022-1139(00)82390-8.
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