Manganese(III) fluoride

Manganese(III) fluoride
	Manganese(III) fluoride
Names
	IUPAC name Manganese(III) fluoride
	Other names Manganese trifluoride, manganic fluoride
Identifiers
CAS Number	7783-53-1 ;
3D model (JSmol)	Interactive image;
ChemSpider	74193 ;
ECHA InfoCard	100.029.096
EC Number	232-006-6;
PubChem CID	82213;
RTECS number	OP0882600;
UNII	VHG84D268X ;
CompTox Dashboard (EPA)	DTXSID50893904 ;
	InChI InChI=1S/3FH.Mn/h31H;/q;;;+3/p-3 Key: SRVINXWCFNHIQZ-UHFFFAOYSA-K ; InChI=1/3FH.Mn/h31H;/q;;;+3/p-3 Key: SRVINXWCFNHIQZ-DFZHHIFOAX;
	SMILES [Mn+3].[F-].[F-].[F-];
Properties
Chemical formula	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)
Solubility in water	hydrolysis
Magnetic susceptibility (χ)	+10,500·10−6 cm3/mol
Structure
Crystal structure	Monoclinic, mS48
Space group	C2/c, No. 15
Coordination geometry	distorted octahedral
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	toxic fumes
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H272, H301, H312, H315, H319, H332, H335
Precautionary statements	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). verify (what is ?) 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.^[2] 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:^[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]

References

^ GHS: sigma-aldrich 339296 ^{[dead link‍]}
^ 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.
^ 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.
^ ^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. ISBN 0-19-855370-6.
^ 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.
^ M. A. Hepworth; K. H. Jack (1957). "The Crystal Structure of Manganese Trifluoride, MnF₃". Acta Crystallographica. 10 (5): 345–351. doi:10.1107/S0365110X57001024.
^ 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.
^ 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)
^ 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
^ 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.
^ 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.
^ Chisholm, Hugh, ed. (1911). "Manganese § Manganic Salts" . Encyclopædia Britannica. Vol. 17 (11th ed.). Cambridge University Press. p. 570.
^ 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
^ 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.

External links

[1] GHS: sigma-aldrich 339296 ^{[dead link‍]}

[eros-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.

[mad-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.

[shap-4] 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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Manganese(III) fluoride

Synthesis, structure and reactions

Structure

Reactions

See also

References

Further reading

External links

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