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Silver(I) fluoride

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"AgF" redirects here. For other uses, see AgF (disambiguation).
Silver(I) fluoride
Names
IUPAC name
Silver(I) fluoride
Other names
Argentous fluoride
Silver monofluoride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.028.996 Edit this at Wikidata
RTECS number
  • VW4250000
UNII
  • [Ag+].[F-]
Properties
AgF
Molar mass 126.8666 g·mol−1
Appearance yellow-brown solid
Density 5.852 g/cm3 (15 °C)
Melting point 435 °C (815 °F; 708 K)
Boiling point 1,159 °C (2,118 °F; 1,432 K)
85.78 g/100 mL (0 °C)
119.8 g/100 mL (10 °C)
179.1 g/100 mL (25 °C)
213.4 g/100 mL (50 °C)[1]
Solubility 83g/100 g (11.9 °C) in hydrogen fluoride
1.5g/100 mL in methanol(25 °C)[2]
−36.5·10−6 cm3/mol
Structure
cubic
Thermochemistry
48.1 J/mol·K[1]
83.7 J/mol·K[1]
-206 kJ/mol[1]
-187.9 kJ/mol[1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Corrosive
GHS labelling:[4]
GHS05: Corrosive
Danger
H314
P260, P280, P303+P361+P353, P304+P340, P305+P351+P338, P310[3]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Safety data sheet (SDS) External SDS
Related compounds
Other anions
 Silver(I) oxide
Silver(I) chloride

Silver(I) bromide
Silver(I) iodide

Other cations
 Copper(I) fluoride
Gold(I) fluoride
Related compounds
 Silver subfluoride
Silver(II) fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Silver(I) fluoride is the inorganic compound with the formula AgF. It is one of the three main fluorides of silver, the others being silver subfluoride and silver(II) fluoride. AgF has relatively few niche applications; it has been employed as a fluorination and desilylation reagent in organic synthesis and in aqueous solution as a topical caries treatment in dentistry.

The hydrates of AgF present as colourless, while pure anhydrous samples are yellow.[5]: 150 

Preparation

High-purity silver(I) fluoride can be produced by the heating of silver carbonate to 310 °C (590 °F) under a hydrogen fluoride environment, in a platinum tube:[6]: 9 

Laboratory routes to the compound typically avoid the use of gaseous hydrogen fluoride. One method is the thermal decomposition of silver tetrafluoroborate:

In an alternative route, silver(I) oxide is dissolved in concentrated aqueous hydrofluoric acid, and the silver fluoride is precipitated out of the resulting solution by acetone.[6]: 10 

Properties

Structure

The structure of AgF has been determined by X-ray diffraction.[7][8]: 3735  At ambient temperature and pressure, silver(I) fluoride exists as the polymorph AgF-I, which adopts a cubic crystal system with space group Fm3m in the Hermann–Mauguin notation. The rock salt structure is adopted by the other silver monohalides. The lattice parameter is 4.936(1) Å, significantly lower than those of AgCl and AgBr.[9]: 562  Neutron and X-ray diffraction studies have further shown that at 2.70(2) GPa, a structural transition occurs to a second polymorph (AgF-II) with the caesium chloride structure, and lattice parameter 2.945 Å.[10]: 7945 [11]: 770  The associated decrease in volume is approximately ten percent.[10]: 7946  A third polymorph, AgF-III, forms on reducing the pressure to 2.59(2) GPa, and has an inverse nickel arsenide structure. The lattice parameters are a = 3.244(2) Å and c = 6.24(1) Å; the rock salt structure is regained only on reduction of the pressure to 0.9(1) GPa. Non-stochiometric behaviour is exhibited by all three polymorphs under extreme pressures.[12]: 939 [10]: 7947 

Spectroscopy

Silver(I) fluoride exhibits unusual optical properties. Simple electronic band theory predicts that the fundamental exciton absorption for AgF would lie higher than that of AgCl (5.10 eV) and would correspond to a transition from an anionic valence band as for the other silver halides. Experimentally, the fundamental exciton for AgF lies at 4.63 eV.[13]: 2604  This discrepancy can be explained by positing transition from a valence band with largely silver 4d-orbital character.[9]: 563  The high frequency refractive index is 1.73(2).[8]: 3737 

Photosensitivity

In contrast with the other silver halides, anhydrous silver(I) fluoride is not appreciably photosensitive, although the dihydrate is.[14]: 286 [5]: 150  With this and the material's solubility in water considered, it is unsurprising that it has found little application in photography but may have been one of the salts used by Levi Hill in his "heliochromy",[15] although a US patent for an experimental AgF-based method was granted in 1970.[16]

Solubility

Unlike the other silver halides, AgF is highly soluble in water (1800 g/L), and it even has some solubility in acetonitrile. It is also unique among silver(I) compounds and the silver halides in that it forms the hydrates AgF·(H2O)2 and AgF·(H2O)4 on precipitation from aqueous solution.[17]: 1185 [18] Like the alkali metal fluorides, it dissolves in hydrogen fluoride to give a conducting solution.[19]

Applications

Organic synthesis

Silver(I) fluoride finds application in organofluorine chemistry for addition of fluoride across multiple bonds. For example, AgF adds to perfluoroalkenes in acetonitrile to give perfluoroalkylsilver(I) derivatives.[20]: 7367  It can also be used as a desulfuration-fluorination reagent on thiourea derived substrates.[18]: 562  Due to its high solubility in water and organic solvents, it is a convenient source of fluoride ions, and can be used to fluorinate alkyl halides under mild conditions.[2] An example is given by the following reaction:[21]

Another organic synthetic method using silver(I) fluoride is the BINAP-AgF complex catalyzed enantioselective protonation of silyl enol ethers:[22]: 1546 

Inorganic synthesis

The reaction of silver acetylide with a concentrated solution of silver(I) fluoride results in the formation of a chandelier-like [Ag10]2+ cluster with endohedral acetylenediide.[23]

Tetralkylammonium fluorides can be conveniently prepared in the laboratory by the reaction of the tetralkylammonium bromide with an aqueous AgF solution.[24]: 430 

Other

It is possible to coat a silicon surface with a uniform silver microlayer (0.1 to 1 μm thickness) by passing AgF vapour over it at 60–800 °C.[25] The relevant reaction is:

Multiple studies have shown silver(I) fluoride to be an effective anti-caries agent, although the mechanism is the subject of current research.[26] Treatment is typically by the "atraumatic" method, in which 40% by mass aqueous silver(I) fluoride solution is applied to carious leisons, followed by sealing of the dentine with glass ionomer cement.[27] Although the treatment is generally recognised to be safe, fluoride toxicity has been a significant clinical concern in paediatric applications, especially as some commercial preparations have had considerable silver(II) fluoride contamination in the past.[27][28][29] Due to the instability of concentrated AgF solutions, silver diamine fluoride (Ag(NH3)2F) is now more commonly used.[29]: 26  Preparation is by the addition of ammonia to aqueous silver fluoride solution or by the dissolution of silver fluoride in aqueous ammonia.[30]

References

  1. ^ a b c d e Chemister Chemical Database, Kiper Ruslan Anatolievich, 2002-15. URL: http://chemister.ru/Database/properties-en.php?dbid=1&id=1067
  2. ^ a b Busse, Juliette K.; Stoner, Eric J. (2001). "Silver (I) fluoride". E-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rs016. ISBN 0471936235.
  3. ^ "Silver Fluoride". American Elements. Retrieved 2018-09-07.
  4. ^ Sigma-Aldrich Co., Silver(I) fluoride. Retrieved on 2014-05-08.
  5. ^ a b Palmer, William George (1954). Experimental Inorganic Chemistry. CUP Archive. ISBN 9780521059022.
  6. ^ a b Roesky, Herbert W. (2012). Efficient Preparation of Fluorine Compounds. Somerset, New Jersey: Wiley. ISBN 9781118409428.
  7. ^ Ott, H. (1926). "XI. Die Strukturen von MnO, MnS, AgF, NiS, SnJ4, SrCl2, BaF2; Präzisionsmessungen einiger Alkalihalogenide". Z. Kristallogr. 63 (1–6): 222–230. doi:10.1524/zkri.1926.63.1.222. S2CID 102244646.
  8. ^ a b Bottger, G.L.; Geddes, A.L. (1972). "Lattice Vibrations, Crystal Structure, Dielectric Properties, and Elastic Constants of AgF". J. Chem. Phys. 56 (8): 3735–3739. Bibcode:1972JChPh..56.3735B. doi:10.1063/1.1677770.
  9. ^ a b Birtcher, R.C.; Deutsch, P.W.; Wendelken, J.F.; Kunz, A.B. (1972). "Valence band structure in silver fluoride". J. Phys. C: Solid State Phys. 5 (5): 562–6. Bibcode:1972JPhC....5..562B. doi:10.1088/0022-3719/5/5/008.
  10. ^ a b c Hull, S.; Berastegui, P (1998). "High-pressure structural behaviour of silver(I) fluoride". J. Phys.: Condens. Matter. 10 (36): 7945–7955. Bibcode:1998JPCM...10.7945H. doi:10.1088/0953-8984/10/36/005.
  11. ^ Halleck, P.M.; Jamieson, J.C. (1972). "B1 and B2 phase change of AgF at high pressure". J. Phys. Chem. Solids. 33 (4): 769–773. Bibcode:1972JPCS...33..769H. doi:10.1016/s0022-3697(72)80093-3.
  12. ^ Jamieson, J.C.; Halleck, P.M.; Roof, R.B.; Pistorius, C.W.F.T. (1975). "Additional polymorphism and non-stoichiometry in AgF". Journal of Physics and Chemistry of Solids. 36 (9): 939–944. Bibcode:1975JPCS...36..939J. doi:10.1016/0022-3697(75)90172-9.
  13. ^ Marchetti, A.P.; Bottger, G.L. (1971). "Optical Absorption Spectrum of AgF". Physical Review B. 3 (8): 2604–7. Bibcode:1971PhRvB...3.2604M. doi:10.1103/physrevb.3.2604.
  14. ^ Slayter, Elizabeth (1992). Light and Electron Microscopy. Cambridge University Press. ISBN 9780521339483.
  15. ^ Hill, Levi L. (1856). A treatise on heliochromy : or, The production of pictures, by means of light, in natural colors. Embracing a full, plain, and unreserved description of the process known as the hillotype, including the author's newly discovered collodio-chrome, or natural colors on collodionized glass ... Getty Research Institute. New York : Robinson & Caswell. p. 143.
  16. ^ US patent 3537855, "Photosensitive silver fluoride element", published 1971-11-3 
  17. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  18. ^ a b Tyrra, Wieland (2002). "Silver(I) fluoride and related compounds in chemical synthesis". Heteroatom Chemistry. 13 (6): 561–566. doi:10.1002/hc.10102.
  19. ^ Schwartz, Mel (2002). Encyclopedia of Materials, Parts and Finishes (2nd ed.). CRC press. p. 305. ISBN 1420017160.
  20. ^ Miller, W. T.; Burnard, R. J. (1968). "Perfluoroalkylsilver compounds" "Title". J. Am. Chem. Soc. 90: 7367–7368. doi:10.1021/ja01028a047.
  21. ^ Muller, Paul; Etienne, Robert; Pfyfer, Jean; Pinenda, Nelson; Schipoff, Michel (1978). "Allylic Reactions of Benzocyclopropenes. Discrimination of Halogen Substituents in 1,l-Dihalogenobenzocyclopropenes". Helvetica Chimica Acta. 61 (7): 2482–8. doi:10.1002/hlca.19780610719.
  22. ^ Yanagisawa, Akira; Touge, Taichiro; Takayoshi, Arai (2005). "Enantioselective Protonation of Silyl Enolates Catalyzed by a Binap⋅AgF Complex". Angewandte Chemie International Edition. 44 (10): 1546–8. doi:10.1002/anie.200462325. PMID 15645475.
  23. ^ Guo, Guo-Cong; Zhou, Gong-Du; Wang, Qi-Guang; Mak, Thomas C.W. (1998). "A Fully Encapsulated Acetylenediide in Ag2C2.8AgF". Angewandte Chemie International Edition. 37 (5): 630–2. doi:10.1002/(sici)1521-3773(19980316)37:5<630::aid-anie630>3.0.co;2-k.
  24. ^ Clark, James H. (1980). "Fluoride ion as a base in organic synthesis". Chemical Reviews. 80 (5): 429–452. doi:10.1021/cr60327a004.
  25. ^ Voorhoeve, R. J. H.; Merewether, J. W. (1972). "Selective Deposition of Silver on Silicon by Reaction with Silver Fluoride Vapor". J. Electrochem. Soc. 119 (3): 364–368. Bibcode:1972JElS..119..364V. doi:10.1149/1.2404203.
  26. ^ Peng, J. J-Y.; Botelho, M.G.; Matinlinna, J.P. (2012). "Silver compounds used in dentistry for caries management: A review". Journal of Dentistry. 40 (7): 531–541. doi:10.1016/j.jdent.2012.03.009. PMID 22484380.
  27. ^ a b Gotjamanos, Theo; Afonso, Fernando (1997). "Unacceptably high levels of fluoride in commercial preparations of silver fluoride". Australian Dental Journal. 42 (1): 52–3. doi:10.1111/j.1834-7819.1997.tb00097.x. PMID 9078648.
  28. ^ Gotjamanos, Theo; Orton, Vergil (1998). "Abnormally high fluoride levels in commercial preparations of 40 per cent silver fluoride solution: Contraindications for use in children". Australian Dental Journal. 43 (6): 422–7. doi:10.1111/j.1834-7819.1998.tb00203.x. PMID 9973713.
  29. ^ a b Shah, Shalin; Bhaskar, Visjay; Venkatraghavan, Karthik; Choudhary, Prashant; Trivedi, Krishna; M., Ganesh (2014). "Silver Diamine Fluoride: A Review and Current Applications". Journal of Advanced Oral Research. 5 (1): 25–35. doi:10.1177/2229411220140106. S2CID 56987580.
  30. ^ US patent 3567823, Yokomizo Ichiro & Yamaga Reiichi, "Silver ammonia fluoride solution and method of its use", published 1971-2-12 
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