Misplaced Pages

Fluorosulfates

Article snapshot taken from Wikipedia with creative commons attribution-sharealike license. Give it a read and then ask your questions in the chat. We can research this topic together.

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. 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, SO4. 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 cm/mol. Most metal ions, and quaternary ammonium ions, can form fluorosulfate salts. 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.

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 However, by the twenty-first century fluorosulfate was superseded in this use, in particular by BARF.

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.

Some pseudoternary fluorosulfates exist including Cs, Cs, Cs2

Related ionic compounds are the fluoroselenites SeO3F and the fluorosulfites SO2F. 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.

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
NOSO3F nitrosyl fluorosulfonate melts 156 density 1.96
NO2SO3F nitronium fluorosulfinate
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
PO(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
Ti(SO3F)4 titanium tetrafluorosulfonate
titanium(IV) fluorosulfonate 		S2O5F2
VO(SO3F)3 deep red liquid
CrO2(SO3F)2 chromyl fluorosulfate green or brown
Mn(SO3F)2
MnO(SO3F) brownish black
Mn(SO3F)3
Mn(CO)4(SO3F)
Mn(CO)5(SO3F)
Rb2Mn(SO3F)5
Cs2Mn(SO3F)5
Fe(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
Cu(SO3F)2 cupric fluorosulfate
copper(II) fluorosulfate 		pale yellow/white 210 S2O5F2
SO3
CuSO4
CuF2
Cu(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
Ga(SO3F)3 gallium fluorosulfate white 240 SO3 polymeric
As(SO3F)3 arsenic trifluorosulfonate
arsenic(III) fluorosulfonate 		S2O5F2
AsF2(SO3F)3
AsF3(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
Nb(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
AgSO3F silver fluorosulfate P21/m a=5.413 b=8.174 c=7.544 β=94.60 V=83.17 Z=4
Ag(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 Å, Z = 4, d = 3.15 gcm
Ag2O(SO3F)2 black
Ag2Ag(SO3F)4 silver(I, II) fluorosulfate black
KAg2Ag(SO3F)5 orthorhombic P 2221, a = 6.4736 b = 7.3915 c = 17.7736
RbAg2Ag(SO3F)5 orthorhombic P 2221, a = 6.4828 b = 7.3551c = 18.0262
RbAg(SO3F)3 monoclinic P 21/m , a = 15.815 b = 15.486 c = 17.021 β = 101.513
CsAg(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
In(SO3F)3 Indium tri(fluorosulfate) polymeric
Sn(SO3F)4 tin tetrafluorosulfonate
tin(IV) fluorosulfonate 		S2O5F2
SbF4SO3F
Sb(SO3F)2.2CH3CN
Cs 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
IF3(SO3F)2 iodine trifluoride bisfluorosulfonate
FXe(SO3F)
Xe(SO3F)2 xenon(II) fluorosulfate
F5Xe(SO3F)
CsSO3F caesium fluorosulfate l41/a a=5.611 b=5.611 c=14.13 V=111.3 Z=4
Cs
Ba(SO3F)2 BaSO4 SO2F2
Ho(SO3F)3 holmium fluorosulfate
Ta(SO3F)5 tantalum pentafluorosulfonate
pentakis(fluorosulfonato)tantalum(V) 		colourless solution
TaO(SO3F)3 yellow liquid
WO(SO3F)4 oxo tetrakis(fluorosulfato)tungsten(VI) colourless liquid
ReO2(SO3F)3 dioxo trisfluorosulfato rhenium(VII) white solid
ReO3(SO3F) trioxo fluorosulfato rhenium(VII) yellow liquid
Re(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 cesium hexakis(fluorosulfato)platinate(IV)
Pt(CO)2(SO3F)2 bis(carbonyl)platinum(II) fluorosulfate creamy white
AuCO(SO3F)
Au(SO3F)2 gold(II) fluorosulfate yellow red
Au(SO3F)3
Cs 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
Tl(SO3F)3 thallium tri(fluorosulfate)
thallium(III) fluorosulfonate
Pb(SO3F)4 lead(IV) fluorosulfate
Bi(SO3F)3 bismuth(III) fluorosulfate
tris(fluorosulfonato)bismuth(III)
Th(SO3F)4 thorium(IV) fluorosulfate
U(SO3F)2 yellow
U(SO3F)3 green
U(SO3F)4 uranium(IV) fluorosulfate tan
Na2U(SO3F)6
UO(SO3F)2 oxouranium(IV) fluorosulfate
UO2(SO3F)2 uranyl fluorosulfate
dioxouranium(VI) fluorosulfate

References

  1. ^ 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. ^ 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. Bibcode:2016JFluC.189..102M. doi:10.1016/j.jfluchem.2016.07.024.
  3. ^ Lawrance, Geoffrey A. (February 1986). "Coordinated trifluoromethanesulfonate and fluorosulfate". Chemical Reviews. 86 (1): 17–33. doi:10.1021/cr00071a002.
  4. ^ Simons, J. H. (1964). Fluorine Chemistry volume 5. Elsevier. pp. 71–72. ISBN 978-0-323-14724-8.
  5. Grice, Joel D.; Gault, Robert A.; Chao, George Y. (1 October 1995). "Reederite-(Y), a new sodium rare-earth carbonate mineral with a unique fluorosulfate anion". American Mineralogist. 80 (9–10): 1059–1064. Bibcode:1995AmMin..80.1059G. doi:10.2138/am-1995-9-1023. S2CID 100079211.
  6. ^ Jache, Albert W. (1974), Fluorosulfuric Acid, Its Salts, and Derivatives, Advances in Inorganic Chemistry and Radiochemistry, vol. 16, Elsevier, pp. 177–200, doi:10.1016/s0065-2792(08)60292-7, ISBN 978-0-12-023616-9
  7. ^ Roberts, John E.; Cady, George H. (January 1960). "The Preparation of Mercury(II), Nitrosyl and Nitronium Fluorosulfonates from Peroxydisulfuryl Difluoride". Journal of the American Chemical Society. 82 (2): 353–354. doi:10.1021/ja01487a024. ISSN 0002-7863.
  8. Barr, J.; Gillespie, J.; Ummat, P.K. (1970). "The cation S4". Journal of the Chemical Society D: Chemical Communications (5): 264. doi:10.1039/C29700000264.
  9. ^ Hayek, E.; Czaloun, A.; Krismer, B. (1956). "Bildung und Zersetzung von Fluorsulfonaten". Monatshefte für Chemie (in German). 87 (6): 741–748. doi:10.1007/BF00899586. ISSN 0026-9247.
  10. Singh, Sukhjinder; Verma, Rajendar D. (January 1983). "Aluminium tris(fluorosulphate)". Polyhedron. 2 (11): 1209–1210. doi:10.1016/S0277-5387(00)84360-0.
  11. A.G. Sharpe; H.J. Emeléus (1976). Advances in inorganic chemistry and radiochemistry Volume 18. : Academic Press. pp. 357–358. ISBN 0-12-023618-4.
  12. Nakamoto, Kazuo (2009-01-16). Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B: Applications in Coordination, Organometallic, and Bioinorganic Chemistry. John Wiley & Sons. p. 89. ISBN 978-0-470-40587-1.
  13. Brown, S. D.; Gard, G. L. (1978-05-01). "Oxidation of some transition metal carbonyls by peroxydisulfuryl difluoride". Inorganic Chemistry. 17 (5): 1363–1364. doi:10.1021/ic50183a052. ISSN 0020-1669.
  14. 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.
  15. ^ Mallela, S. P.; Aubke, F. (September 1985). "Fluorosulfate derivatives of manganese and rhenium". Inorganic Chemistry. 24 (19): 2969–2975. doi:10.1021/ic00213a020. ISSN 0020-1669.
  16. ^ 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.
  17. ^ Alleyne, Carl S.; Thompson, Robert C. (1974-09-15). "Coordinating Properties of the Fluorosulfate Ion. Tetrakis(pyridine) Complexes of Zinc(II), Copper(II), and Nickel(II) Fluorosulfates". Canadian Journal of Chemistry. 52 (18): 3218–3228. doi:10.1139/v74-474. ISSN 0008-4042.
  18. Storr, A.; Yeats, P. A.; Aubke, F. (1972-02-01). "Gallium(III)-trisfluorosulfate". Canadian Journal of Chemistry. 50 (3): 452–454. doi:10.1139/v72-068. ISSN 0008-4042.
  19. 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.
  20. ^ Emme, Larry (2000-01-01). "Synthesis of Uranium Fluorosulfates and the Group VI B Difluorophosphates". Dissertations and Theses. doi:10.15760/etd.1593.
  21. ^ 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.
  22. ^ Leung, Patrick C.; Aubke, Friedhelm (1984-12-01). "Fluorosulfates of the noble metals. Part 6. Synthesis and magnetic properties of fluorosulfato compounds of ruthenium". Canadian Journal of Chemistry. 62 (12): 2892–2897. doi:10.1139/v84-489. ISSN 0008-4042.
  23. ^ Leung, P.C.; Wong, G.B.; Aubke, F. (May 1987). "Fluorosulfates of the noble metals, Part 7: The tris fluorosulfates of osmium and rhodium". Journal of Fluorine Chemistry. 35 (4): 607–620. doi:10.1016/S0022-1139(00)81959-4.
  24. ^ Lee, K. C.; Aubke, F. (1977-07-01). "Fluorosulfates of palladium". Canadian Journal of Chemistry. 55 (13): 2473–2477. doi:10.1139/v77-338. ISSN 0008-4042.
  25. ^ Hwang, G.; Wang, C.; Bodenbinder, M.; Willner, H.; Aubke, F. (February 1994). "The syntheses and vibrational spectra of bis(carbonyl)platinum(II) fluorosulfate, Pt(CO)2(SO3F)2, and bis(carbonyl)palladium(II) fluorosulfate, Pd(CO)2(SO3F)2". Journal of Fluorine Chemistry. 66 (2): 159–166. doi:10.1016/0022-1139(93)03013-C.
  26. Wang, Changqing; Bodenbinder, Matthias; Willner, Helge; Rettig, Steven; Trotter, James; Aubke, Friedhelm (February 1994). "Synthesis, Molecular Structure, and Vibrational Spectra of cyclo-Bis(.mu.-carbonyl)dipalladium(I) Fluorosulfate, (SO3F)2". Inorganic Chemistry. 33 (4): 779–786. doi:10.1021/ic00082a026. ISSN 0020-1669.
  27. ^ 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.
  28. ^ Michałowski, T.; Mazej, Z.; Budzianowski, A.; Jagličić, Z.; Leszczyński, P. J.; Grochala, W. (January 2015). "Unexpectedly Complex Crystalline Phases in the MSO 3 F-Ag(SO 3 F) 2 Phase Diagram (M = Na, K, Rb, Cs): Complex Crystalline Phases". European Journal of Inorganic Chemistry. 2015 (2): 324–332. doi:10.1002/ejic.201402948.
  29. ^ 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. doi:10.1016/0022-1902(81)80409-5.
  30. ^ Zhang, Dingliang; Rettig, Steven J.; Trotter, James; Aubke, Friedhelm (January 1996). "Superacid Anions: Crystal and Molecular Structures of Oxonium Undecafluorodiantimonate(V), , Cesium Fluorosulfate, CsSO 3 F, Cesium Hydrogen Bis(fluorosulfate), Cs, Cesium Tetrakis(fluorosulfato)aurate(III), Cs, Cesium Hexakis(fluorosulfato)platinate(IV), Cs 2 , and Cesium Hexakis(fluorosulfato)antimonate(V), Cs". Inorganic Chemistry. 35 (21): 6113–6130. doi:10.1021/ic960525l. ISSN 0020-1669.
  31. ^ Yeats, P.A; Wilson, W.W; Aubke, F (February 1973). "Dibromoiodine(III)-and dichloroiodine(III)-fluorosulfate". Inorganic and Nuclear Chemistry Letters. 9 (2): 209–214. doi:10.1016/0020-1650(73)80057-1.
  32. Aubke, Friedhelm; Cady, George H.; Kennard, C. H. L. (December 1964). "Iodyl Fluorosulfate". Inorganic Chemistry. 3 (12): 1799–1800. doi:10.1021/ic50022a041. ISSN 0020-1669.
  33. Johnson, Wesley M.; Macklin, John W. (May 1976). "Vibration spectra and structure of lanthanide fluorosulfate compounds". Inorganic Chemistry. 15 (5): 1216–1220. doi:10.1021/ic50159a049. ISSN 0020-1669.
  34. Dev, Rajendar.; Cady, George H. (May 1972). "Synthesis and characterization of oxotetrakis(fluorosulfato)tungsten(VI)". Inorganic Chemistry. 11 (5): 1134–1135. doi:10.1021/ic50111a046. ISSN 0020-1669.
  35. ^ Wang, Changqing; Lewis, Andrew R.; Batchelor, Raymond J.; Einstein, Frederick W. B.; Willner, Helge; Aubke, Friedhelm (January 1996). "Synthesis, Molecular Structure, and Vibrational Spectra of mer -Tris(carbonyl)iridium(III) Fluorosulfate, mer -Ir(CO) 3 (SO 3 F) 3". Inorganic Chemistry. 35 (5): 1279–1285. doi:10.1021/ic9506769. ISSN 0020-1669. PMID 11666319.
  36. ^ Lee, Keith C.; Aubke, Friedhelm (January 1982). "Fluorosulfates of the noble metals, part 4 fluorosulfates of iridium". Journal of Fluorine Chemistry. 19 (3–6): 501–516. Bibcode:1982JFluC..19..501L. doi:10.1016/S0022-1139(00)83149-8.
  37. 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. Bibcode:1991JFluC..52...13W. doi:10.1016/S0022-1139(00)80318-8.
  38. Carter, Henry A.; Charles A. Milne; F. Aubke (1975). "Lead (IV) fluorosulphate". Journal of Inorganic and Nuclear Chemistry. 37 (1): 282–283. doi:10.1016/0022-1902(75)80170-9.(not consulted)
  39. 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. 17 (3): 273–275.(not consulted)
  40. ^ 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. Bibcode:1980JFluC..16..153P. doi:10.1016/S0022-1139(00)82390-8.
Categories: