Manganese(III) fluoride

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Manganese(III) fluoride
Manganese(III) fluoride Manganese-trifluoride-from-xtal-unit-cell-3D-bs-17.png
Manganese(III) fluoride
Manganese(III) fluoride.png
Names
IUPAC name
Manganese(III) fluoride
Other names
Manganese trifluoride, manganic fluoride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.096 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 232-006-6
PubChem CID
RTECS number
  • OP0882600
UNII
  • InChI=1S/3FH.Mn/h3*1H;/q;;;+3/p-3 Yes check.svgY
    Key: SRVINXWCFNHIQZ-UHFFFAOYSA-K Yes check.svgY
  • InChI=1/3FH.Mn/h3*1H;/q;;;+3/p-3
    Key: SRVINXWCFNHIQZ-DFZHHIFOAX
  • [Mn+3].[F-].[F-].[F-]
Properties
MnF3
Molar mass 111.938 g/mol
Appearancepurple-pink powder
hygroscopic
Density 3.54 g/cm3
Melting point >600 °C (1,112 °F; 873 K) (decomposes)
hydrolysis
+10,500·10−6 cm3/mol
Structure
Monoclinic, mS48
C2/c, No. 15
distorted octahedral
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
toxic fumes
GHS labelling: [1]
GHS-pictogram-rondflam.svg GHS-pictogram-skull.svg
Danger
H272, H301, H312, H315, H319, H332, H335
P220, P261, P280, P301+P310, P305+P351+P338
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).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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. [2] It forms a hydrate and many derivatives.

Contents

Synthesis, structure and reactions

MnF3 can be prepared by treating a solution of MnF2 in hydrogen fluoride with fluorine: [3]

MnF2 + 0.5 F2 → MnF3

It can also be prepared by the reaction of elemental fluorine with a manganese(II) halide at ~250 °C. [4]

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. [5] [6] [7]

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]− ). [8]

Reactions

MnF3 is Lewis acidic and forms a variety of derivatives. One example is K2MnF3(SO4). [9] MnF3 reacts with sodium fluoride to give the octahedral hexafluoride: [4]

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. [4]

Manganese(III) fluoride fluorinates organic compounds including aromatic hydrocarbons, [10] cyclobutenes, [11] and fullerenes. [12]

On heating, MnF3 decomposes to manganese(II) fluoride. [13] [14]

MnF3 is a source of MnCl3 complexes by reaction with bismuth trichloride. [15]

See also

Related Research Articles

In chemistry, halogenation is a chemical reaction which introduces one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

<span class="mw-page-title-main">Praseodymium(III) chloride</span> Chemical compound

Praseodymium(III) chloride is the inorganic compound with the formula PrCl3. Like other lanthanide trichlorides, it exists both in the anhydrous and hydrated forms. It is a blue-green solid that rapidly absorbs water on exposure to moist air to form a light green heptahydrate.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.

<span class="mw-page-title-main">Nickel(II) fluoride</span> Chemical compound

Nickel(II) fluoride is the chemical compound with the formula NiF2. It is an ionic compound of nickel and fluorine and forms yellowish to green tetragonal crystals. Unlike many fluorides, NiF2 is stable in air.

<span class="mw-page-title-main">Bromine trifluoride</span> Chemical compound

Bromine trifluoride is an interhalogen compound with the formula BrF3. At room temperature, it is a straw-coloured liquid with a pungent odor which decomposes violently on contact with water and organic compounds. It is a powerful fluorinating agent and an ionizing inorganic solvent. It is used to produce uranium hexafluoride (UF6) in the processing and reprocessing of nuclear fuel.

<span class="mw-page-title-main">Chromium(III) fluoride</span> Chemical compound

Chromium(III) fluoride is an inorganic compound with the chemical formula CrF3. It forms several hydrates. The compound CrF3 is a green crystalline solid that is insoluble in common solvents, but the hydrates [Cr(H2O)6]F3 (violet) and [Cr(H2O)6]F3·3H2O (green) are soluble in water. The anhydrous form sublimes at 1100–1200 °C.

<span class="mw-page-title-main">Cobalt(III) fluoride</span> Chemical compound

Cobalt(III) fluoride is the inorganic compound with the formula CoF3. Hydrates are also known. The anhydrous compound is a hygroscopic brown solid. It is used to synthesize organofluorine compounds.

<span class="mw-page-title-main">Cobalt(II) fluoride</span> Chemical compound

Cobalt(II) fluoride is a chemical compound with the formula (CoF2). It is a pink crystalline solid compound which is antiferromagnetic at low temperatures (TN=37.7 K) The formula is given for both the red tetragonal crystal, (CoF2), and the tetrahydrate red orthogonal crystal, (CoF2·4H2O). CoF2 is used in oxygen-sensitive fields, namely metal production. In low concentrations, it has public health uses. CoF2 is sparingly soluble in water. The compound can be dissolved in warm mineral acid, and will decompose in boiling water. Yet the hydrate is water-soluble, especially the di-hydrate CoF2·2H2O and tri-hydrate CoF2·3H2O forms of the compound. The hydrate will also decompose with heat.

<span class="mw-page-title-main">Iron(III) fluoride</span> Chemical compound

Iron(III) fluoride, also known as ferric fluoride, are inorganic compounds with the formula FeF3(H2O)x where x = 0 or 3. They are mainly of interest by researchers, unlike the related iron(III) chloride. Anhydrous iron(III) fluoride is white, whereas the hydrated forms are light pink.

Antimony pentafluoride is the inorganic compound with the formula SbF5. This colourless, viscous liquid is a strong Lewis acid and a component of the superacid fluoroantimonic acid, formed upon mixing liquid HF with liquid SbF5 in 1:1 ratio. It is notable for its strong Lewis acidity and the ability to react with almost all known compounds.

<span class="mw-page-title-main">Hexafluorosilicic acid</span> Octahedric silicon compound

Hexafluorosilicic acid is an inorganic compound with the chemical formula H
2SiF
6. Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.

<span class="mw-page-title-main">Selenium tetrafluoride</span> Chemical compound

Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

<span class="mw-page-title-main">Antimony trifluoride</span> Chemical compound

Antimony trifluoride is the inorganic compound with the formula SbF3. Sometimes called Swarts' reagent, it is one of two principal fluorides of antimony, the other being SbF5. It appears as a white solid. As well as some industrial applications, it is used as a reagent in inorganic and organofluorine chemistry.

<span class="mw-page-title-main">Manganese(IV) fluoride</span> Chemical compound

Manganese tetrafluoride, MnF4, is the highest fluoride of manganese. It is a powerful oxidizing agent and is used as a means of purifying elemental fluorine.

Arsenic trifluoride is a chemical compound of arsenic and fluorine with the chemical formula AsF3. It is a colorless liquid which reacts readily with water. Like other inorganic arsenic compounds, it is highly toxic.

Polyhalogen ions are a group of polyatomic cations and anions containing halogens only. The ions can be classified into two classes, isopolyhalogen ions which contain one type of halogen only, and heteropolyhalogen ions with more than one type of halogen.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

<span class="mw-page-title-main">Platinum tetrafluoride</span> Chemical compound

Platinum tetrafluoride is the inorganic compound with the chemical formula PtF
4. In the solid state, the compound features platinum(IV) in octahedral coordination geometry.

<span class="mw-page-title-main">Rhodium trifluoride</span> Chemical compound

Rhodium(III) fluoride or rhodium trifluoride is the inorganic compound with the formula RhF3. It is a red-brown, diamagnetic solid.

References

  1. ↑ GHS: sigma-aldrich 339296 [ dead link ]
  2. ↑ Burley, G. A.; Taylor, R. (2004). "Manganese(III) Fluoride". Encyclopedia of Reagents for Organic Synthesis. J. Wiley & Sons. doi:10.1002/047084289X.rn00411. ISBN   0-471-93623-5.
  3. ↑ 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.
  4. 1 2 3 Inorganic chemistry, Catherine E. Housecroft, A.G. Sharpe, pp.711-712, section Manganese (III) , googlebooks link
  5. ↑ Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN   0-19-855370-6.
  6. ↑ Hepworth, M. A.; Jack, K. H.; Nyholm, R. S. (1957). "Interatomic Bonding in Manganese Trifluoride". Nature . 179 (4552): 211–212. Bibcode:1957Natur.179..211H. doi:10.1038/179211b0. S2CID   4208409.
  7. ↑ M. A. Hepworth; K. H. Jack (1957). "The Crystal Structure of Manganese Trifluoride, MnF3". Acta Crystallographica. 10 (5): 345–351. doi:10.1107/S0365110X57001024.
  8. ↑ 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.
  9. ↑ Bhattacharjee, M. N; Chaudhuri, M. K. (2007). "Dipotassium Trifluorosulfato-Manganate(III)". Inorganic Syntheses. Vol. 27. pp. 312–313. doi:10.1002/9780470132586.ch61. ISBN   978-0-470-13258-6.{{cite book}}: |journal= ignored (help)
  10. ↑ Fluorination of p-chlorobenzotrifluoride by manganese trifluoride Archived 2011-08-23 at the Wayback Machine A. Kachanov, V. Kornilov, V.Belogay , Fluorine Notes :Vol. 1 (1) November–December 1998 , via notes.fluorine1.ru
  11. ↑ Junji Mizukado; Yasuhisa Matsukawa; Heng-dao Quan; Masanori Tamura; Akira Sekiya (2006). "Fluorination of Fluoro-Cyclobutene with High-Valency Metal Fluoride". Journal of Fluorine Chemistry. 127: 79–84. doi:10.1016/j.jfluchem.2005.10.007.
  12. ↑ V. É. Aleshina; A. Ya. Borshchevskii; E. V. Skokan; I. V. Arkhangel'skii; A.V. Astakhov; N.B. Shustova (2002). "Fluorination of the Cubic and Hexagonal C60 Modifications by Crystalline Manganese Trifluoride". Physics of the Solid State. 44 (4): 629–630. Bibcode:2002PhSS...44..629A. doi:10.1134/1.1470543. S2CID   94250136.
  13. ↑ Chisholm, Hugh, ed. (1911). "Manganese § Manganic Salts"  . Encyclopædia Britannica . Vol. 17 (11th ed.). Cambridge University Press. p. 570.
  14. ↑ 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
  15. ↑ Nachtigall, Olaf; Pataki, Astrid; Molski, Matthias; Lentz, Dieter; Spandl, Johann (2015). "Solvates of Manganese Trichloride Revisited - Synthesis, Isolation, and Crystal Structure of MnCl3(THF)3". Zeitschrift für Anorganische und Allgemeine Chemie. 641 (6): 1164–1168. doi:10.1002/zaac.201500106.

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