Tin(II) fluoride

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Stannous fluoride
Names
IUPAC name
Tin(II) fluoride
Other names
Stannous fluoride
Identifiers
ECHA InfoCard 100.029.090 Edit this at Wikidata
RTECS number
  • XQ3450000
UN number 3288
Properties
SnF2
Molar mass 156.69 g/mol
Appearance colorless solid
Density 4.57 g/cm3
Melting point 215°C
Boiling point 850°C
ca. 350 g/l (20°C)
Related compounds
Other anions
 Tin(II) chloride
Tin(II) bromide
Tin(II) iodide
Other cations
 Germanium tetrafluoride
Tin tetrafluoride
Lead(II) fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Tin(II) fluoride, also known as stannous fluoride, is the chemical compound with the formula SnF2. This colourless solid is a common ingredient in toothpaste. In the enamel, it converts apatite into fluoroapatite, which is more resistant to attack by acids generated by bacteria. Sodium fluoride and sodium fluorophosphate perform similarly. Stannous fluoride can be mixed with calcium abrasives while the more common sodium fluoride gradually becomes biologically inactive combined with calcium.[1] It has also been shown to be more effective than sodium fluoride in controlling gingivitis.[2]

Stannous fluoride was used (under the trade name Fluoristan) in the original formulation of the toothpaste Crest[citation needed]., though it was later replaced with sodium monofluorophosphate[citation needed]. However it is the active ingredient in Crest Pro Health brand toothpaste according to the label on the box and the tube. Crest Pro Health also issues a warning on the tube that stannous fluoride may cause staining; and that by proper brushing this can be avoided; and that their particular formulation is resistant to staining.

Used in combination with abrasives that contain calcium, sodium fluoride is ineffective; stannous fluoride remains effective when used with such abrasives. Stannous fluoride can cause surface staining of teeth, but these stains are not permanent.

SnF2 can be prepared by evaporating a solution of SnO in 40% HF.[3]

Aqueous solutions

Readily soluble in water SnF2 is hydrolysed forming at low concentration species such as SnOH+, Sn(OH)2 and Sn(OH)3− and at higher concentrations, predominantly polynuclear species, Sn2(OH)22+ and Sn3(OH)42+.[4]Aqueous solutions readily oxidise to form insoluble precipitates of SnIV which are ineffective as a dental prophylactic. [5] Studies of the oxidation using Mössbauer spectroscopy on frozen samples suggests that O2 is the oxidizing species.[6]

Lewis acidity

SnF2 is a Lewis acid forming, for example, a 1:1 complex (CH3)3NSnF2 and 2:1 complex [(CH3)3N]2SnF2 with trimethylamine[7], and a 1:1 complex with dimethylsulfoxide, (CH3)2SO.SnF2.[8]
In solutions containing fluoride ion, F− it forms fluoride complexes SnF3−, Sn2F5−, SnF2(OH2).[9] Crystallization from an aqueous solution containing NaF produces compounds containing polynuclear anions, e.g. NaSn2F5 or Na4Sn3F10 depending on the reaction conditions, rather than NaSnF3[3]producing NaSnF3 The compound NaSnF3 containing the pyramidal SnF3− anion can however be produced from a pyridine - water solution.[10] Other compounds containing the pyramidal SnF3− anion are known for example Ca(SnF3)2 [11]

Reducing properties

SnF2 is a reducing agent, with a standard reduction potential Eo (SnIV/ SnII) = +0.15V [12].Solutions in HF are readily oxidised by a range of oxidizing agents, O2, SO2 or F2, to form the mixed valence compound, Sn3F8 (containing SnII and SnIV and no Sn - Sn bonds).[3]

Structure

The monoclinic form contains tetramers, Sn4F8, where there are two distinct coordination environments for the Sn atoms but in each case there are three nearest neighbours with Sn at the apex of a trigonal pyramid and the lone pair of electrons is sterically active.[13] Other forms reported have the GeF2 and TeO2 structures.[13]

Molecular SnF2

In the vapour phase SnF2 forms monomers as well as dimers and trimers.[9] Monomeric SnF2 is a non-linear molecule with an Sn-F bond length of 206 pm.[9]
Complexes of SnF2, sometimes called difluorostannylene, with an alkyne and aromatic compounds deposited in an argon matrix at 12 K have been reported [14] [15]

References

  1. ^ Hattab, F. (April 1989). "The State of Fluorides in Toothpastes". Journal of Dentistry. 17 (2): 47–54. doi:10.1016/0300-5712(89)90129-2. PMID 2732364.
  2. ^ "The clinical effect of a stabilized stannous fluoride dentifrice on plaque formation, gingivitis and gingival bleeding: a six-month study". The Journal of Clinical Dentistry. 6 (Special Issue): 54–58. 1995. PMID 8593194.
  3. ^ a b c Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  4. ^ Séby F., Potin-Gautier M., Giffaut E., Donard O. F. X. (2001). "A critical review of thermodynamic data for inorganic tin species". Geochimica et Cosmochimica Acta. 65 (18): 3041–3053. doi:10.1016/S0016-7037(01)00645-7.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. ^ David B. Troy, 2005, Remington: The Science and Practice of Pharmacy, Lippincott Williams & Wilkins, ISBN 0781746736, 9780781746731
  6. ^ Denes G; Lazanas G. (1994). "Oxidation of SnF2 stannous fluoride in aqueous solutions". Hyperfine Interactions. 90 (1): 435–439. doi:10.1007/BF02069152.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  7. ^ Chung Chun Hsu and R. A. Geanangel (1977). "Synthesis and studies of trimethylamine adducts with tin(II) halides". Inorg. Chem. 16 (1): 2529–2534. doi:10.1021/ic50176a022.
  8. ^ Chung Chun Hsu and R. A. Geanangel (1980). "Donor and acceptor behavior of divalent tin compounds". Inorg. Chem. 19 (1): 110–119. doi:10.1021/ic50203a024.
  9. ^ a b c Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0123526515
  10. ^ Salami T.O. , Zavalij P.Y. and Oliver S.R.J. (2004). "Synthesis and crystal structure of two tin fluoride materials: NaSnF3 (BING-12) and Sn3F3PO4". Journal of Solid State Chemistry. 177 (3): 800–805. doi:10.1016/j.jssc.2003.09.013.
  11. ^ Kokunov Y.V., Detkov D. G., Gorbunova Yu. E.,Ershova M. M. , Mikhailov Yu. N. (2001). "Synthesis and Crystal Structure of Calcium Trifluorostannate(II)". Doklady Chemistry. 376 (4–6): 52–54. doi:10.1023/A:1018855109716.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  12. ^ Catherine E. Housecroft, A. G. Sharpe, 2005, Inorganic Chemistry, Pearson Education, ISBN 0130399132
  13. ^ a b Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
  14. ^ S. E. Boganov, V. I. Faustov, M. P. Egorov and O. M. Nefedov (1994). "Matrix IR spectra and quantum chemical studies of the reaction between difluorostannylene and hept-1-yne. The first direct observation of a carbene analog π-complex with alkyne". Russian Chemical Bulletin Volume. 43 (1): 47–49. doi:10.1007/BF00699133.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  15. ^ S. E. Boganov, M. P. Egorov and O. M. Nefedov (1999). "Study of complexation between difluorostannylene and aromatics by matrix IR spectroscopy". Russian Chemical Bulletin. 48 (1): 98–103. doi:10.1007/BF02494408.
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