Fluorosulfates

The parent acid, fluorosulfuric acid.

The fluorosulfates or fluorosulfonates are a set of salts of fluorosulfuric acid containing the fluorosulfonate anion SO3F−. The fluorosulfate anion can be treated as though it were a hydrogen sulfate anion with hydroxyl substituted by fluorine. The fluorosulfate ion has a low propensity to form complexes with metal cations. Since fluorine is similar in size to oxygen, the fluorosulfate ion is roughly tetrahedral and forms salts similar to those of the perchlorate ion. It is isoelectronic with sulfate, SO2−4. When an organic group is substituted for the anions, organic fluorosulfonates are formed.

In solution the fluorosulfate anion is completely ionised. The volume of the ions is 47.8 cm3/mol. Quaternary ammonium and most metal ions can form fluorosulfate salts. Different ways to make these salts include treating a metal chloride with anhydrous fluorosulfuric acid, releasing hydrogen chloride gas. Double decomposition methods utilising a metal sulfate with barium fluorosulfate, or a metal chloride with silver fluorosulfate, leave the metal salt in solution.

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 However, by the twenty-first century fluorosulfate was superseded in this use, in particular by BARF.

Many pseudobinary fluorosulfate salts are known. They are called pseudobinary because, although there is one other element, there are four kinds of atoms. Nonmetal pseudobinary fluorosulfates are known for including those of halogens and xenon.

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

Fluoroselenates (SeO3F−) are unknown as of 2023. Known related compounds include fluorooxotellurates, hydroxyfluorooxotellurates, fluorochromates (CrO3F−), fluoroselenites (SeO2F−) and fluorosulfites (SO2F−). Sulfate fluorides are distinct, as they contain fluoride ions without a bond to the sulfate groups.

There exists one fluorosulfate mixed anion compound, which also contains carbonate and chloride, containing mineral called reederite-(Y).

Compounds

Formula Name Colour Decomposition temperature (°C) Decomposition product Crystal Ref
LiSO3F lithium fluorosulfate C2/m a=8.54 b=7.62 c=4.98 β=90.0 V=81
Be(SO3F)2 SO3
CF3(SO3F)
CF2(SO3F)2
CF(SO3F)3
C(SO3F)4
NH4SO3F ammonium fluorosulfate Orthorhombic Pnma a=8.97 b=6.00 c=7.54 V=101.4 Z=4
N(CH3)4SO3F tetramethylammonium fluorosulfate Orthorhombic Pnma a=8.38 b=8.38 c=5.86 V=102.88 Z=4
NIIIOSO3F nitrosyl fluorosulfonate melts 156 density 1.96
NVO2SO3F nitronium fluorosulfinate
C(NH2)3SO3F guanidinium fluorosulfinate SHQ: 5 × KDP; birefringence: 0.133@1064 nm
S4(SO3F)2 tetrasulfur fluorosulfate
S2O6F2 bis(fluorosulfuryl) peroxide
NaSO3F sodium fluorosulfate Hexagonal a=5.4812 b=5.4812 c=6.5172 V=169.57 Z=2 D=2.390
Mg(SO3F)2 magnesium fluorosulfonate SO3
Al(SO3F)2.3CH3CN
Al(SO3F)3 aluminium fluorosulfate white polymeric, fluorosulfate is bidentate and bridged
Si(SO3F)4 silicon tetrafluorosulfonate S2O5F2
SiO2
PVO(SO3F)3 phosphoryl trifluorosulfonate S2O5F2
PO(SO3F)
ClSO3F chlorosulfuryl fluoride
ClO2SO3F chloryl fluorosulfate red or pale yellow low melting point
KSO3F potassium fluorosulfate Pnma a=8.62 b=5.84 c=7.35 V=92.5
Ca(SO3F)2 CaF2 SO3
TiIV(SO3F)4 titanium tetrafluorosulfonate
titanium(IV) fluorosulfonate		 S2O5F2
VO(SO3F)3 deep red liquid
CrVIO2(SO3F)2 chromyl fluorosulfate green or brown
Mn(SO3F)2
MnO(SO3F) brownish black
Mn(SO3F)3
MnI(CO)4(SO3F)
MnI(CO)5(SO3F)
Rb2Mn(SO3F)5
Cs2Mn(SO3F)5
FeIII(SO3F)3 ferric fluorosulfate green grey 230 S2O5F2
SO3
FeF3
CoO(SO3F) chocolate brown
Ni(SO3F)2
Ni(py)4(SO3F)2 py=pyridine
NiO(SO3F) dark grey
CuII(SO3F)2 cupric fluorosulfate
copper(II) fluorosulfate		 pale yellow/white 210 S2O5F2
SO3
CuSO4
CuF2
CuII(py)4(SO3F)2 py=pyridine
Cu(SO3F).CH3CN
Zn(SO3F)2 zinc fluorosulfate white 280 SO3
ZnF2
Zn(py)4(SO3F)2 py=pyridine
GaIII(SO3F)3 gallium fluorosulfate white 240 SO3 polymeric
AsIII(SO3F)3 arsenic trifluorosulfonate
arsenic(III) fluorosulfonate		 S2O5F2
AsVF2(SO3F)3
AsVF3(SO3F)2
BrSO3F bromosulfuryl fluoride red liquid
RbSO3F rubidium fluorosulfate Orthorhombic Pnma a=8.7812 b=6.0318 c=7.5108 V=397.82 Z=4 D=3.081
Sr(SO3F)2 SO2F2
MoO2(SO3F)2
NbV(SO3F)5 niobium pentafluorosulfonate
niobium(V) fluorosulfate		 colourless solution 25 SO3
NbO(SO3F)3 yellow liquid
Ru(SO3F)3 very dark red
CsRu(SO3F)4 dark brown
ClO2Ru(SO3F)4 black
CsRu(SO3F)5 red brown
Cs2Ru(SO3F)6 bright orange
K2Ru(SO3F)6 bright orange
Rh(SO3F)3 bright orange 190
Pd(SO3F)2 purple 250 SO3 PdF2
Pd(SO3F)3 dark brown 180
Pd(CO)2(SO3F)2 bis(carbonyl)palladium(II) fluorosulfate yellow
c-Pd2(μ-CO)2](SO3F)2 cyclo-Bis(μ-carbonyl)dipalladium(I) Fluorosulfate orange monoclinic C2/c a=11.495 b=8.255 c=9.556 β =91.94 Z=8
AgISO3F silver fluorosulfate P21/m a=5.413 b=8.174 c=7.544 β=94.60 V=83.17 Z=4
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° V =643.88 Å3, Z = 4, d = 3.15 gcm−3
Ag2O(SO3F)2 black
AgI2AgII(SO3F)4 silver(I, II) fluorosulfate black
KAgI2AgII(SO3F)5 orthorhombic P 2221, a = 6.4736 b = 7.3915 c = 17.7736
RbAgI2AgII(SO3F)5 orthorhombic P 2221, a = 6.4828 b = 7.3551c = 18.0262
RbAgII(SO3F)3 monoclinic P 21/m , a = 15.815 b = 15.486 c = 17.021 β = 101.513
CsAgII(SO3F)3 triclinic P1_ , a = 14.9241 b = 9.7046 c = 17.8465 α = 109.116°, β = 84.655° γ = 119.171°
Cd(SO3F)2
InIII(SO3F)3 Indium tri(fluorosulfate) polymeric
SnIV(SO3F)4 tin tetrafluorosulfonate
tin(IV) fluorosulfonate		 S2O5F2
SbF4SO3F
Sb(SO3F)2.2CH3CN
Cs[Sb(SO3F)6] Cesium hexakis(fluorosulfato)antimonate(V) trigonal, R3̄ a = 12.0317 Å, c = 12.026 Å, Z = 3
TeF5SO3F
ISO3F
ICl2SO3F
IBr2SO3F rust brown 90 ISO3F, Br2
IO2SO3F iodyl fluorosulfate 100 yellow
IVF3(SO3F)2 iodine trifluoride bisfluorosulfonate
FXe(SO3F)
XeII(SO3F)2 xenon(II) fluorosulfate
F5XeVI(SO3F)
CsSO3F caesium fluorosulfate l41/a a=5.611 b=5.611 c=14.13 V=111.3 Z=4
Cs[H(SO3F)2]
Ba(SO3F)2 BaSO4 SO2F2
Ho(SO3F)3 holmium fluorosulfate
TaV(SO3F)5 tantalum pentafluorosulfonate
pentakis(fluorosulfonato)tantalum(V)		 colourless solution
TaVO(SO3F)3 yellow liquid
WVIO(SO3F)4 oxo tetrakis(fluorosulfato)tungsten(VI) colourless liquid
ReVIIO2(SO3F)3 dioxo trisfluorosulfato rhenium(VII) white solid
ReVIIO3(SO3F) trioxo fluorosulfato rhenium(VII) yellow liquid
ReI(CO)5(SO3F)
Os(SO3F)3 bright green 130
Ir(SO3F)3
Ir(SO3F)4
Cs2Ir(SO3F)6
BaIr(SO3F)6
(ClO2)2Ir(SO3F)6
mer-Ir(CO)3(SO3F)3 mer-Tris(carbonyl)iridium(III) Fluorosulfate colourless Monoclinic P21/c, Z = 4, a = 8.476 b = 12.868 c = 12.588 β = 108.24°, V = 1304.0 MW 573.42
Pt(SO3F)4
Cs2[Pt(SO3F)6] cesium hexakis(fluorosulfato)platinate(IV)
Pt(CO)2(SO3F)2 bis(carbonyl)platinum(II) fluorosulfate creamy white
AuICO(SO3F)
AuII(SO3F)2 gold(II) fluorosulfate yellow red
AuIII(SO3F)3
Cs[Au(SO3F)4] Cesium Tetrakis(fluorosulfato)aurate(III) monoclinic, C2/c a = 17.725 Å, b = 5.822 Å, c = 14.624 Å, β = 102.120°, Z = 4
Hg(SO3F)2 mercuric fluorosulfate density 3.715
TlSO3F thallium fluorosulfate Orthorhombic a=5.2205 b=5.5141 c=13.4378 V=386.83 Z=4 D=5.210
TlO(SO3F) brown
TlIII(SO3F)3 thallium tri(fluorosulfate)
thallium(III) fluorosulfonate
PbIV(SO3F)4 lead(IV) fluorosulfate
BiIII(SO3F)3 bismuth(III) fluorosulfate
tris(fluorosulfonato)bismuth(III)
ThIV(SO3F)4 thorium(IV) fluorosulfate
UII(SO3F)2 yellow
UIII(SO3F)3 green
UIV(SO3F)4 uranium(IV) fluorosulfate tan
Na2UIV(SO3F)6
UIVO(SO3F)2 oxouranium(IV) fluorosulfate
UVIO2(SO3F)2 uranyl fluorosulfate
dioxouranium(VI) fluorosulfate

References

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