Difference between revisions of "Manganese tetrafluoride"
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==Preparation== | ==Preparation== | ||
| − | Manganese tetrafluoride was first unequivocally prepared in 1961{{#tag:ref|Reports of the preparation of MnF<sub>4</sub> date back to the nineteenth century,<ref>{{citation | first = W. H. | last = Melville | title = Contribution towards the History of the Fluorides of Manganese | journal = Proc. Am. Acad. Arts Sci. | volume = 12 | year = 1876 | pages = 228–34 | url = http://www.jstor.org/stable/25138452}}.</ref> but are inconsistent with the now-known chemistry of the genuine compound. However, the more stable hexafluoromanganate(IV) compounds were prepared as early as 1899.<ref>{{citation | first1 = R. F. | last1 = Weinland | first2 = O. | last2 = Lauenstein | journal = Z. Anorg. Allg. Chem. | year = 1899 | volume = 20 | page = 40}}.</ref>|group=Note}} by the reaction of [[manganese(II) fluoride]] (or other Mn<sup>II</sup> compounds) with a stream of [[fluorine]] gas at 550 °C: the MnF<sub>4</sub> sublimes into the gas stream and condenses onto a [[cold finger]].<ref>{{citation | title = Mangantetrafluorid, MnF<sub>4</sub> | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | journal = Naturwissenschaften | year = 1961 | volume = 48 | issue = 11 | page = 429 | doi = 10.1007/BF00621676}}.</ref><ref>{{citation | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | title = Mangantetrafluorid mit einem Anhang über LiMnF<sub>5</sub> und LiMnF<sub>4</sub> | journal = Justus Liebigs Ann. Chem. | volume = 658 | issue = 1 | pages = 1–5 | year = 1962 | doi = 10.1002/jlac.19626580102}}.</ref> This is | + | Manganese tetrafluoride was first unequivocally prepared in 1961{{#tag:ref|Reports of the preparation of MnF<sub>4</sub> date back to the nineteenth century,<ref>{{citation | first = W. H. | last = Melville | title = Contribution towards the History of the Fluorides of Manganese | journal = Proc. Am. Acad. Arts Sci. | volume = 12 | year = 1876 | pages = 228–34 | url = http://www.jstor.org/stable/25138452}}.</ref> but are inconsistent with the now-known chemistry of the genuine compound. However, the more stable hexafluoromanganate(IV) compounds were prepared as early as 1899.<ref>{{citation | first1 = R. F. | last1 = Weinland | first2 = O. | last2 = Lauenstein | journal = Z. Anorg. Allg. Chem. | year = 1899 | volume = 20 | page = 40}}.</ref>|group=Note}} by the reaction of [[manganese(II) fluoride]] (or other Mn<sup>II</sup> compounds) with a stream of [[fluorine]] gas at 550 °C: the MnF<sub>4</sub> sublimes into the gas stream and condenses onto a [[cold finger]].<ref>{{citation | title = Mangantetrafluorid, MnF<sub>4</sub> | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | journal = Naturwissenschaften | year = 1961 | volume = 48 | issue = 11 | page = 429 | doi = 10.1007/BF00621676}}.</ref><ref>{{citation | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | title = Mangantetrafluorid mit einem Anhang über LiMnF<sub>5</sub> und LiMnF<sub>4</sub> | journal = Justus Liebigs Ann. Chem. | volume = 658 | issue = 1 | pages = 1–5 | year = 1962 | doi = 10.1002/jlac.19626580102}}.</ref> This is still the commonest method of preparation, although the sublimation can be avoided by operating at increased fluorine pressure (4.5–6 bar at 180–320 °C) and mechanically agitating the powder to avoid sintering of the grains.<ref name="AstorPrepn"/><ref name="SolvayPrepn">{{citation | inventor1-last = Seseke-Koyro | inventor1-first = Ulrich | inventor2-last = Garcia-Juan | inventor2-first = Placido | inventor3-last = Palsherm | inventor3-first = Stefan | inventor4-last = Schulz | inventor4-first = Alf | assignee = Solvay Fluor | title = Method for preparing manganese tetrafluoride | country-code = WO | description = PCT Appl. | publication-number = 2009074560 | publication-date = 2009-06-18}}.</ref> The reaction can also be carried out starting from [[manganese]] powder in a [[fluidized bed]].<ref>{{citation | first1 = H. | last1 = Roesky | first2 = O. | last2 = Glemser | title = A New Preparation of Manganese Tetrafluoride | journal = Angew. Chem., Int. Ed. Engl. | volume = 2 | issue = 10 | page = 626 | year = 1963 | doi = 10.1002/anie.196306262}}.</ref><ref>{{citation | first1 = Herbert W. | last1 = Roesky | first2 = Oskar | last2 = Glemser | first3 = Karl-Heinz | last3 = Hellberg | title = Darstellung von Metallfluoriden in der Wirbelschicht | journal = Chem. Ber. | volume = 98 | issue = 6 | pages = 2046–48 | year = 1965 | doi = 10.1002/cber.19650980642}}.</ref> |
Other preparations of MnF<sub>4</sub> include the fluorination of MnF<sub>2</sub> with [[krypton difluoride]],<ref>{{citation | first1 = Karel | last1 = Lutar | first2 = Adolf | last2 = Jesih | first3 = Boris | last3 = Žemva | title = KrF<sub>2</sub>/MnF<sub>4</sub> adducts from KrF<sub>2</sub>/MnF<sub>2</sub> interaction in HF as a route to high purity MnF<sub>4</sub> | journal = Polyhedron | volume = 7 | issue = 13 | year = 1988 | pages = 1217–19 | doi = 10.1016/S0277-5387(00)81212-7}}.</ref> or with F<sub>2</sub> in liquid [[hydrogen fluoride]] solution under [[ultraviolet light]].<ref>{{citation | first = Z. | last = Mazej | title = Room temperature syntheses of MnF<sub>3</sub>, MnF<sub>4</sub> and hexafluoromanganete(IV) salts of alkali cations | journal = J. Fluorine Chem. | volume = 114 | issue = 1 | year = 2002 | pages = 75–80 | doi = 10.1016/S0022-1139(01)00566-8}}.</ref> Manganese tetrafluoride has also been prepared (but not isolated) in an acid–base reaction between [[antimony pentafluoride]] and K<sub>2</sub>MnF<sub>6</sub> as part of a chemical synthesis of elemental fluorine.<ref>{{citation | first = Karl O. | last = Christe | year = 1986 | title = Chemical synthesis of elemental fluorine | journal = Inorg. Chem. | volume = 25 | issue = 21 | pages = 3721–24 | doi = 10.1021/ic00241a001}}.</ref> | Other preparations of MnF<sub>4</sub> include the fluorination of MnF<sub>2</sub> with [[krypton difluoride]],<ref>{{citation | first1 = Karel | last1 = Lutar | first2 = Adolf | last2 = Jesih | first3 = Boris | last3 = Žemva | title = KrF<sub>2</sub>/MnF<sub>4</sub> adducts from KrF<sub>2</sub>/MnF<sub>2</sub> interaction in HF as a route to high purity MnF<sub>4</sub> | journal = Polyhedron | volume = 7 | issue = 13 | year = 1988 | pages = 1217–19 | doi = 10.1016/S0277-5387(00)81212-7}}.</ref> or with F<sub>2</sub> in liquid [[hydrogen fluoride]] solution under [[ultraviolet light]].<ref>{{citation | first = Z. | last = Mazej | title = Room temperature syntheses of MnF<sub>3</sub>, MnF<sub>4</sub> and hexafluoromanganete(IV) salts of alkali cations | journal = J. Fluorine Chem. | volume = 114 | issue = 1 | year = 2002 | pages = 75–80 | doi = 10.1016/S0022-1139(01)00566-8}}.</ref> Manganese tetrafluoride has also been prepared (but not isolated) in an acid–base reaction between [[antimony pentafluoride]] and K<sub>2</sub>MnF<sub>6</sub> as part of a chemical synthesis of elemental fluorine.<ref>{{citation | first = Karl O. | last = Christe | year = 1986 | title = Chemical synthesis of elemental fluorine | journal = Inorg. Chem. | volume = 25 | issue = 21 | pages = 3721–24 | doi = 10.1021/ic00241a001}}.</ref> | ||
Revision as of 10:02, 12 September 2010
| Manganese tetrafluoride | |
|---|---|
| IUPAC name | manganese tetrafluoride |
| Other names | manganese(IV) fluoride |
| Identifiers | |
| InChI | InChI=1/4FH.Mn/h4*1H;/q;;;;+4/p-4 |
| Standard InChI | InChI=1S/4FH.Mn/h4*1H;/q;;;;+4/p-4 |
| Standard InChIKey | KWKYNMDHPVYLQQ-UHFFFAOYSA-J |
| CAS number | [] |
| Properties | |
| Chemical formula | MnF4 |
| Molar mass | 130.93 g mol−1 |
| Appearance | blue solid |
| Melting point |
70 °C decomp. |
| Solubility in water | reacts violently |
| Related compounds | |
| Other cations | Manganese(II) fluoride Manganese(III) fluoride |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) | |
Manganese tetrafluoride, MnF4, is the highest fluoride of manganese. It is used as a powerful oxidizing agent and as a means of purifying elemental fluorine.[1][2]
Contents
Preparation
Manganese tetrafluoride was first unequivocally prepared in 1961[Note 1] by the reaction of manganese(II) fluoride (or other MnII compounds) with a stream of fluorine gas at 550 °C: the MnF4 sublimes into the gas stream and condenses onto a cold finger.[5][6] This is still the commonest method of preparation, although the sublimation can be avoided by operating at increased fluorine pressure (4.5–6 bar at 180–320 °C) and mechanically agitating the powder to avoid sintering of the grains.[1][7] The reaction can also be carried out starting from manganese powder in a fluidized bed.[8][9]
Other preparations of MnF4 include the fluorination of MnF2 with krypton difluoride,[10] or with F2 in liquid hydrogen fluoride solution under ultraviolet light.[11] Manganese tetrafluoride has also been prepared (but not isolated) in an acid–base reaction between antimony pentafluoride and K2MnF6 as part of a chemical synthesis of elemental fluorine.[12]
- K2MnF6 + 2 SbF5 → MnF4 + 2 KSbF6
Chemistry
Decomposition
Other reactions
Applications
Fluoromanganate(IV) complexes
Notes and references
Notes
References
- ↑ 1.0 1.1 Torisu, Junichi; Oka, Masakazu; Kuznetsov, Andrey Sergeyevich, et al. (Astor Electronics/Showa Denko) Method of manufacturing manganese tetrafluoride. WO PCT Appl. 2006033480, published 30 March 2006.
- ↑ Seseke-Koyro, Ulrich; Garcia-Juan, Placido; Palsherm, Stefan, et al. (Solvay Fluor) Process for the purification of elemental fluorine. WO PCT Appl. 2009074562, published 18 June 2009.
- ↑ Melville, W. H. Contribution towards the History of the Fluorides of Manganese. Proc. Am. Acad. Arts Sci. 1876, 12, 228–34, <http://www.jstor.org/stable/25138452>.
- ↑ Weinland, R. F.; Lauenstein, O. Z. Anorg. Allg. Chem. 1899, 20, 40.
- ↑ Hoppe, Rudolf; Dähne, Wolfgang; Klemm, Wilhelm Mangantetrafluorid, MnF4. Naturwissenschaften 1961, 48 (11), 429. DOI: 10.1007/BF00621676.
- ↑ Hoppe, Rudolf; Dähne, Wolfgang; Klemm, Wilhelm Mangantetrafluorid mit einem Anhang über LiMnF5 und LiMnF4. Justus Liebigs Ann. Chem. 1962, 658 (1), 1–5. DOI: 10.1002/jlac.19626580102.
- ↑ Seseke-Koyro, Ulrich; Garcia-Juan, Placido; Palsherm, Stefan, et al. (Solvay Fluor) Method for preparing manganese tetrafluoride. WO PCT Appl. 2009074560, published 18 June 2009.
- ↑ Roesky, H.; Glemser, O. A New Preparation of Manganese Tetrafluoride. Angew. Chem., Int. Ed. Engl. 1963, 2 (10), 626. DOI: 10.1002/anie.196306262.
- ↑ Roesky, Herbert W.; Glemser, Oskar; Hellberg, Karl-Heinz Darstellung von Metallfluoriden in der Wirbelschicht. Chem. Ber. 1965, 98 (6), 2046–48. DOI: 10.1002/cber.19650980642.
- ↑ Lutar, Karel; Jesih, Adolf; Žemva, Boris KrF2/MnF4 adducts from KrF2/MnF2 interaction in HF as a route to high purity MnF4. Polyhedron 1988, 7 (13), 1217–19. DOI: 10.1016/S0277-5387(00)81212-7.
- ↑ Mazej, Z. Room temperature syntheses of MnF3, MnF4 and hexafluoromanganete(IV) salts of alkali cations. J. Fluorine Chem. 2002, 114 (1), 75–80. DOI: 10.1016/S0022-1139(01)00566-8.
- ↑ Christe, Karl O. Chemical synthesis of elemental fluorine. Inorg. Chem. 1986, 25 (21), 3721–24. DOI: 10.1021/ic00241a001.
Further reading
- Gubkina, N. I.; Sokolov, Sergey V.; Krylov, E. I. Fluorides of High Oxidising Power and Their Application to the Preparation of Organic Fluorine Compounds. Russ. Chem. Rev. 1966, 35 (12), 930–41. DOI: 10.1070/RC1966v035n12ABEH001550.
- Ehlert, T. C.; Hsia, M. Mass spectrometric and thermochemical studies of the manganese fluorides. J. Fluorine Chem. 1972, 2 (1), 33–51. DOI: 10.1016/S0022-1139(00)83113-9.
- Hoppe, R.; Müller, B.; Burgess, J.; Peacock, R. D.; Sherry, R. The enthalpy of formation of manganese tetrafluoride. J. Fluorine Chem. 1980, 16 (2), 189–91. DOI: 10.1016/S0022-1139(00)82393-3.
- Adelhelm, M.; Jacob, E. MnF4: preparation and properties. J. Fluorine Chem. 1991, 54 (1–3), 21. DOI: 10.1016/S0022-1139(00)83531-9.
External links
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