Manganese(III) fluoride

Manganese(III) fluoride
Names
IUPAC name
Manganese(III) fluoride
Other names
Manganese trifluoride, manganic fluoride
Identifiers
7783-53-1 YesY
3D model (Jmol) Interactive image
ChemSpider 74193 YesY
ECHA InfoCard 100.029.096
PubChem 82213
RTECS number OP0882600
Properties
MnF3
Molar mass 111.938 g/mol
Appearance purple-pink powder
hygroscopic
Density 3.54 g/cm3
Melting point > 600 °C (1,112 °F; 873 K) (decomposes)
hydrolysis
Structure
Monoclinic, mS48
C2/c, No. 15
distorted octahedral
Hazards
Main hazards toxic fumes
R-phrases 8-20/21/22-36/37/38
S-phrases 17-26-36/37/39
Related compounds
Other anions
 manganese(III) oxide, manganese(III) acetate
Other cations
 chromium(III) fluoride, iron(III) fluoride. cobalt(III) fluoride
Related compounds
 manganese(II) fluoride, manganese(IV) 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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Infobox references

Manganese(III) fluoride (also known as Manganese trifluoride) is the inorganic compound with the formula MnF3. This red/purplish solid is useful for converting hydrocarbons into fluorocarbons, i.e., it is a fluorination agent.[1] It also forms a hydrate.

Synthesis, structure and reactions

Synthesis

MnF3 can be prepared by treating a solution of MnF2 in hydrogen fluoride with fluorine:[2]

MnF2 + 0.5 F2 → MnF3

It can also be prepared by the reaction of elemental fluorine with a manganese(II) halide at ~250 °C.[3]

Structure

In the crystalline state, MnF3 resembles vanadium(III) fluoride: both feature octahedral metal centers with the same average M-F bond distances. In the Mn compound, however, is distorted (and hence a monoclinic unit cell vs. a higher symmetry one) due to the Jahn-Teller effect, with pairs of Mn-F distances of 1.79, 1.91, 2.09 Å.[4][5][6]

The hydrate MnF3.3H2O is obtained by crystallisation of MnF3 from hydrofluoric acid. The hydrate is unusual in that it forms two different structures (both based on [Mn(H2O)4F2]+ [Mn(H2O)2F4]− ), which have space groups P21/c and P21/a.[7]

Reactions

MnF3 reacts with sodium fluoride to give the octahedral hexafluorate anion:[3]

3NaF + MnF3 → Na3MnF6

Other reaction conditions give compounds with anion formula MnF52− or MnF4−. These anions are chain and layer structures respectively, with bridging fluorine. Manganese remains 6 coordinate, octahedral, and trivalent in all these materials.[3]

Manganese(III) fluoride fluorinates organic compounds including aromatic hydrocarbons,[8] cyclobutenes,[9] and fullerenes.[10]

On heating, MnF3 decomposes to manganese(II) fluoride.[11][12]

Other manganese(III) compounds include manganese(III) acetate (CAS# 993-02-2), manganese acetylacetonate (CAS# 14284-89-0), Both are employed as oxidants in organic synthesis. MnF3 is Lewis acidic and forms a variety of derivatives. Two examples are K2MnF3(SO4)[13] and K2MnF5.

Safety considerations

Like other reactive inorganic fluorides, MnF3 should be stored in a polyethylene bottle and contact with skin or any other moist area avoided due to the formation of Hydrofluoric acid on hydrolysis.

See also

References

  1. ↑ Burley, G. A.; Taylor, R. "Manganese(III) fluoride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289
  2. ↑ Z. Mazej (2002). "Room temperature syntheses of MnF3, MnF4 and hexafluoromanganete(IV) salts of alkali cations". Journal of Fluorine Chemistry. 114 (1): 75–80. doi:10.1016/S0022-1139(01)00566-8.
  3. 1 2 3 Inorganic chemistry, Catherine E. Housecroft, A.G. Sharpe, pp.711-712, section Manganese (III) , googlebooks link
  4. ↑ Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.
  5. ↑ Hepworth, M. A.; Jack, K. H.; Nyholm, R. S. (1957). "Interatomic Bonding in Manganese Trifluoride". Nature. 179 (4552): 211–212. doi:10.1038/179211b0.
  6. ↑ M. A. Hepworth; K. H. Jack (1957). "The crystal structure of manganese trifluoride, MnF3". Acta Crystallographica. 10 (5): 345–351. doi:10.1107/S0365110X57001024.
  7. ↑ Molinier Michel; Massa Werner (1992). "Structures of two polymorphs of MnF3·3H2O". Journal of Fluorine Chemistry. 57 (1-3): 139–146. doi:10.1016/S0022-1139(00)82825-0.
  8. ↑ Fluorination of p-chlorobenzotrifluoride by manganese trifluoride A. Kachanov, V. Kornilov, V.Belogay , Fluorine Notes :Vol. 1 (1) November–December 1998 , via notes.fluorine1.ru
  9. ↑ Fluorination of fluoro-cyclobutene with high-valency metal fluoride m Junji Mizukado, Yasuhisa Matsukawa, Heng-dao Quan, Masanori Tamura, Akira Sekiya , Journal of Fluorine Chemistry Volume 127, Issue 1, January 2006, Pages 79-84 , online abstract via www.sciencedirect.com
  10. ↑ Fluorination of the cubic and hexagonal C60 modifications by crystalline manganese trifluoride , Physics of the Solid State , Volume 44, Number 4 , 4/2002 , pp.629-630 , V.É. Aleshina, A.Ya. Borshchevskii, E.V. Skokan, I.V. Arkhangel’skii, A.V. Astakhov, N.B. Shustova , online abstract via www.springerlink
  11. ↑ Manganese; section Manganic Salts via www.1911encyclopedia.org
  12. ↑ In situ time-resolved X-ray diffraction study of manganese trifluoride thermal decomposition , J.V. Raua, V. Rossi Albertinib, N.S. Chilingarova, S. Colonnab, U. Anselmi Tamburini, Journal of Fluorine Chemistry 4506 (2001) 1–4 , online version
  13. ↑ Bhattacharjee, M. N; Chaudhuri, M. K. (1990). "Dipotassium Trifluorosulfatomanganate(III)". Inorg. Synth. 27: 312–313. doi:10.1002/9780470132586.ch61.

Further reading

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