Fluorosulfates

The fluorosulfates or fluorosulfonates are a set of salts of fluorosulfuric acid with an ion formula SO3F−. The fluorosulfate anion can be treated 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 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, SO-20−
4.[2] 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.[3] Most metal ions, and quaternary ammonium ions, can form fluorosulfate salts.[3] Different ways to make these salts include treating a metal chloride with anhydrous fluorosulfuric acid, which releases 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.[3]

The fluorosulfate anion is weakly coordinating, and is 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 However, by the twenty-first century fluorosulfate was superseded in this use, in particular by BARF.[2]

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 including those of halogens and xenon.[2]

Some pseudoternary 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] The sulfate fluorides are distinct, as they contain fluoride ions without a bond to the sulfate groups.

One fluorosulfate containing mineral called reederite-(Y) exists. It is a mixed anion compound that also contains carbonate and chloride.[5]

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 [1]
Be(SO3F)2 SO3 [6]
CF3(SO3F) [6]
CF2(SO3F)2 [6]
CF(SO3F)3 [6]
C(SO3F)4 [6]
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]
NIIIOSO3F nitrosyl fluorosulfonate melts 156 density 1.96 [4][7]
NVO2SO3F nitronium fluorosulfinate [7]
S2O6F2 bis(fluorosulfuryl) peroxide [2]
NaSO3F sodium fluorosulfate Hexagonal a=5.4812 b=5.4812 c=6.5172 V=169.57 Z=2 D=2.390 [1]
Mg(SO3F)2 magnesium fluorosulfonate SO3 [4]
Al(SO3F)2.3CH3CN [8]
Al(SO3F)3 aluminium fluorosulfate white polymeric, fluorosulfate is bidentate and bridged [9]
Si(SO3F)4 silicon tetrafluorosulfonate S2O5F2
SiO2		 [4]
PVO(SO3F)3 phosphoryl trifluorosulfonate S2O5F2 [4]
PO(SO3F) [6]
ClSO3F chlorosulfuryl fluoride [2]
ClO2SO3F chloryl fluorosulfate red or pale yellow low melting point [10]
KSO3F potassium fluorosulfate Pnma a=8.62 b=5.84 c=7.35 V=92.5 [1]
Ca(SO3F)2 CaF2 SO3 [6]
TiIV(SO3F)4 titanium tetrafluorosulfonate
titanium(IV) fluorosulfonate		 S2O5F2 [4]
VO(SO3F)3 deep red liquid
CrVIO2(SO3F)2 chromyl fluorosulfate green or brown [11]
Mn(SO3F)2 [6]
MnO(SO3F) brownish black [6]
Mn(SO3F)3 [12]
MnI(CO)4(SO3F) [12]
MnI(CO)5(SO3F) [12]
Rb2Mn(SO3F)5 [12]
Cs2Mn(SO3F)5 [12]
FeIII(SO3F)3 ferric fluorosulfate green grey 230 S2O5F2
SO3
FeF3		 [13]
CoO(SO3F) chocolate brown [6]
Ni(SO3F)2 [6]
Ni(py)4(SO3F)2 py=pyridine [14]
NiO(SO3F) dark grey [6]
CuII(SO3F)2 cupric fluorosulfate
copper(II) fluorosulfate		 pale yellow/white 210 S2O5F2
SO3
CuSO4
CuF2		 [13]
CuII(py)4(SO3F)2 py=pyridine [14]
Cu(SO3F).CH3CN [8]
Zn(SO3F)2 zinc fluorosulfate white 280 SO3
ZnF2		 [13]
Zn(py)4(SO3F)2 py=pyridine [14]
GaIII(SO3F)3 gallium fluorosulfate white 240 SO3 polymeric [15][16]
AsIII(SO3F)3 arsenic trifluorosulfonate
arsenic(III) fluorosulfonate		 S2O5F2 [4]
AsVF2(SO3F)3 [6]
AsVF3(SO3F)2 [6]
BrSO3F bromosulfuryl fluoride red liquid [2]
RbSO3F rubidium fluorosulfate Orthorhombic Pnma a=8.7812 b=6.0318 c=7.5108 V=397.82 Z=4 D=3.081 [1]
Sr(SO3F)2 SO2F2 [6]
MoO2(SO3F)2 [17]
NbV(SO3F)5 niobium pentafluorosulfonate
niobium(V) fluorosulfate		 colourless solution 25 SO3 [18]
NbO(SO3F)3 yellow liquid [17]
Ru(SO3F)3 very dark red [19]
CsRu(SO3F)4 dark brown [19]
ClO2Ru(SO3F)4 black [19]
CsRu(SO3F)5 red brown [19]
Cs2Ru(SO3F)6 bright orange [19]
K2Ru(SO3F)6 bright orange [19]
Rh(SO3F)3 bright orange 190 [20]
Pd(SO3F)2 purple 250 SO3 PdF2 [21]
Pd(SO3F)3 dark brown 180 [21]
Pd(CO)2(SO3F)2 bis(carbonyl)palladium(II) fluorosulfate yellow [22]
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 [23]
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° V =643.88 Å3, Z = 4, d = 3.15 gcm−3 [24]
Ag2O(SO3F)2 black [6]
AgI2AgII(SO3F)4 silver(I, II) fluorosulfate black [24]
KAgI2AgII(SO3F)5 orthorhombic P 2221, a = 6.4736 b = 7.3915 c = 17.7736 [25]
RbAgI2AgII(SO3F)5 orthorhombic P 2221, a = 6.4828 b = 7.3551c = 18.0262 [25]
RbAgII(SO3F)3 monoclinic P 21/m , a = 15.815 b = 15.486 c = 17.021 β = 101.513 [25]
CsAgII(SO3F)3 triclinic P1_ , a = 14.9241 b = 9.7046 c = 17.8465 α = 109.116°, β = 84.655° γ = 119.171° [25]
Cd(SO3F)2 [6]
InIII(SO3F)3 Indium tri(fluorosulfate) polymeric [26]
SnIV(SO3F)4 tin tetrafluorosulfonate
tin(IV) fluorosulfonate		 S2O5F2 [4]
SbF4SO3F [6]
Sb(SO3F)2.2CH3CN [8]
Cs[Sb(SO3F)6] Cesium hexakis(fluorosulfato)antimonate(V) trigonal, R3̄ a = 12.0317 Å, c = 12.026 Å, Z = 3 [27]
TeF5SO3F [6]
ISO3F [28]
ICl2SO3F [28]
IBr2SO3F rust brown 90 ISO3F, Br2 [28]
IO2SO3F iodyl fluorosulfate 100 yellow [29]
IVF3(SO3F)2 iodine trifluoride bisfluorosulfonate [4]
FXe(SO3F) [6]
XeII(SO3F)2 xenon(II) fluorosulfate [2]
F5XeVI(SO3F) [6]
CsSO3F caesium fluorosulfate l41/a a=5.611 b=5.611 c=14.13 V=111.3 Z=4 [1]
Cs[H(SO3F)2] [27]
Ba(SO3F)2 BaSO4 SO2F2 [6]
Ho(SO3F)3 holmium fluorosulfate [30]
TaV(SO3F)5 tantalum pentafluorosulfonate
pentakis(fluorosulfonato)tantalum(V)		 colourless solution [18]
TaVO(SO3F)3 yellow liquid [17]
WVIO(SO3F)4 oxo tetrakis(fluorosulfato)tungsten(VI) colourless liquid [17][31]
ReVIIO2(SO3F)3 dioxo trisfluorosulfato rhenium(VII) white solid [17]
ReVIIO3(SO3F) trioxo fluorosulfato rhenium(VII) yellow liquid [17]
ReI(CO)5(SO3F) [12]
Os(SO3F)3 bright green 130 [20]
Ir(SO3F)3 [32]
Ir(SO3F)4 [33]
Cs2Ir(SO3F)6 [33]
BaIr(SO3F)6 [33]
(ClO2)2Ir(SO3F)6 [33]
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 [32]
Pt(SO3F)4 [22]
Cs2[Pt(SO3F)6] cesium hexakis(fluorosulfato)platinate(IV) [27]
Pt(CO)2(SO3F)2 bis(carbonyl)platinum(II) fluorosulfate creamy white [22]
AuICO(SO3F) [22]
AuII(SO3F)2 gold(II) fluorosulfate yellow red [34]
AuIII(SO3F)3 [22]
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 [27]
Hg(SO3F)2 mercuric fluorosulfate density 3.715 [13]
TlSO3F thallium fluorosulfate Orthorhombic a=5.2205 b=5.5141 c=13.4378 V=386.83 Z=4 D=5.210 [1]
TlO(SO3F) brown [6]
TlIII(SO3F)3 thallium tri(fluorosulfate)
thallium(III) fluorosulfonate		 [26]
PbIV(SO3F)4 lead(IV) fluorosulfate [18][35]
BiIII(SO3F)3 bismuth(III) fluorosulfate
tris(fluorosulfonato)bismuth(III)		 [18][36]
ThIV(SO3F)4 thorium(IV) fluorosulfate [18]
UII(SO3F)2 yellow [17]
UIII(SO3F)3 green [17]
UIV(SO3F)4 uranium(IV) fluorosulfate tan [18][37]
Na2UIV(SO3F)6 [17]
UIVO(SO3F)2 oxouranium(IV) fluorosulfate [37]
UVIO2(SO3F)2 uranyl fluorosulfate
dioxouranium(VI) fluorosulfate		 [37]

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