Manganese(III) fluoride
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| Template:Longitem | MnF3 |
| Molar mass | 111.938 g/mol |
| Appearance | purple-pink powder hygroscopic |
| Density | 3.54 g/cm3 |
| Melting point | Template:Chembox CalcTemperatures |
| Template:Longitem | +10,500·10−6 cm3/mol |
| Template:Longitem | Monoclinic, mS48 |
| Template:Longitem | C2/c, No. 15 |
| Template:Longitem | distorted octahedral |
| Template:Longitem | manganese(III) oxide, manganese(III) acetate |
| Template:Longitem | chromium(III) fluoride, iron(III) fluoride. cobalt(III) fluoride |
| Template:Longitem | manganese(II) fluoride, manganese(IV) fluoride |
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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 forms a hydrate and many derivatives.
Synthesis, structure and reactions
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
Like vanadium(III) fluoride, MnF3 features 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 exists as two polymorphs, with space groups P21/c and P21/a. Each consists of the salt [Mn(H2O)4F2]+[Mn(H2O)2F4]− ).[7]
Reactions
MnF3 is Lewis acidic and forms a variety of derivatives. One example is K2MnF3(SO4).[8] MnF3 reacts with sodium fluoride to give the octahedral hexafluoride:[3]
- 3NaF + MnF3 → Na3MnF6
Related reactions salts of the anions MnF52− or MnF4−. These anions adopt chain and layer structures respectively, with bridging fluoride. Manganese remains 6 coordinate, octahedral, and trivalent in all of these materials.[3]
Manganese(III) fluoride fluorinates organic compounds including aromatic hydrocarbons,[9] cyclobutenes,[10] and fullerenes.[11]
On heating, MnF3 decomposes to manganese(II) fluoride.[12][13]
MnF3 is a source of MnCl3 complexes by reaction with bismuth trichloride.[14]
See also
- CoF3, another fluorinating agent based on a transition metal in an oxidising +3 state.
References
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- ↑ a b c Inorganic chemistry, Catherine E. Housecroft, A.G. Sharpe, pp.711-712, section Manganese (III) , googlebooks link
- ↑ Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. Template:ISBN.
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- ↑ Fluorination of p-chlorobenzotrifluoride by manganese trifluoride Template:Webarchive A. Kachanov, V. Kornilov, V.Belogay , Fluorine Notes :Vol. 1 (1) November–December 1998 , via notes.fluorine1.ru
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- ↑ Template:Cite EB1911
- ↑ 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
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Further reading
- Novel syntheses of some binary fluorides: the role of anhydrous hydrogen fluoride Acta Chim. Slov. 1999, 46(2), pp. 229–238, Zoran Mazej, Karel Lutar and Boris Žemva
- Knudsen Cell mass spectrometry study of Manganese Trifluoride vaporisation, High temperature corrosion and materials chemistry IV: proceedings of the International Symposium, pp. 521–525, google books