六氟化鉑

六氟化鉑
	IUPAC名; Platinum hexafluoride
別名	氟化鉑(VI)
識別
CAS編號	13693-05-5
PubChem	22238670
ChemSpider	2283064
SMILES	F[Pt](F)(F)(F)(F)F;
InChI	1S/6FH.Pt/h6*1H;/q;;;;;;+2/p-6;
EINECS	237-214-0
性質
化學式	PtF6
摩爾質量	309.1 g·mol⁻¹
外觀	暗紅色易揮發性的固體; 蒸氣為類似溴的紅棕色
密度	5.21 g/cm3（計算）; 3.826 g/cm3（液態，64.3 °C）
熔點	61.3 °C
沸點	69.1 °C
溶解性（水）	水解
結構
晶體結構	正交晶系
空間群	Pnma (No. 62)
晶格常數	a = 937.4 pm, b = 852.7 pm, c = 493.3 pm
危險性
主要危害	氧化性
相關物質
相關化學品	六氟合鉑酸氙
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

六氟化鉑，又稱氟化鉑(VI)，化學式為Pt F₆。它是一個深紅色的揮發性固體，氣態時則變成紅棕色。該化合物中鉑的氧化態為+6，只有四個d電子，呈順磁性，基態時為三線態。PtF₆是很強的氧化劑和氟化劑，甚至可以氧化氙，造就第一個貴氣體化合物六氟合鉑酸氙的發現。

合成

PtF₆首次由金屬鉑與氟氣化合製備，^[4]此反應至今仍是首選方法。^[3]

Pt + 3 F₂ → PtF₆

此外，六氟化鉑也可由PtF₅在130 °C下歧化得到，^[5]而反應物PtF₅可由氟化PtCl₂製得。^[6]

2 PtCl₂ + 5 F₂ → 2 PtF₅ + 2 Cl₂

2 PtF₅ → PtF₆ + PtF₄

性質

六氟化鉑是暗紅色晶體，^[1]蒸汽則呈紅棕色，在200 °C下仍然穩定。^[5]固態和氣態六氟化鉑都為八面體構型，Pt-F鍵長為185 pm。^[3]

反應

PtF₆是強氧化劑，甚至可以和氙反應，生成六氟合鉑酸氙（XePtF₆）。1962年發現的此反應證明了貴氣體也能形成化合物。^[7]此外，PtF₆也可以氧化氧氣，生成含有二氧基（O₂⁺）的化合物六氟合鉑酸氧（O₂PtF₆）。^[8]它劇烈水解，生成[PtF₆]^2-，並放出氧氣。^[9]

PtF₆能和三氟化溴、四氟化鎿、四氟化鈈反應，分別生成五氟化溴、六氟化鎿、六氟化鈈。^[2]它還能和亞硝酰氟、硝酰氟、四氧化二氮反應，分別生成NOPtF₆、NO₂PtF₆、N₂O₃PtF₆。^[10]PtF₆也會和一氧化氮反應，產生NOPtF₆，但無法和一氧化二氮反應。^[10]

它和氯酰氟^[11]或五氟化氯^[12]反應，生成六氟合氯(VII)鎓鹽。它和氟化銫在氟化氫里反應，生成CsPtF₆，並放出氟氣。^[13]

參考資料

^ ^1.0 ^1.1 ^1.2 ^1.3 Lide, David R. (編). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英語：CRC Press）. 2009: 4–81. ISBN 978-1-4200-9084-0 （英語）.
^ ^2.0 ^2.1 ^2.2 ^2.3 Weinstock, Bernard; Malm, John G.; Weaver, E. Eugene. The Preparation and Some Properties of Platinum Hexafluoride. Journal of the American Chemical Society (American Chemical Society (ACS)). 1961, 83 (21): 4310–4317. ISSN 0002-7863. doi:10.1021/ja01482a002.
^ ^3.0 ^3.1 ^3.2 ^3.3 Drews, Thomas; Supeł, Joanna; Hagenbach, Adelheid; Seppelt, Konrad. Solid State Molecular Structures of Transition Metal Hexafluorides. Inorganic Chemistry (American Chemical Society (ACS)). 2006-03-28, 45 (9): 3782–3788. ISSN 0020-1669. doi:10.1021/ic052029f.
^ Weinstock, Bernard; Claassen, Howard H.; Malm, John G. Platinum Hexafluoride. Journal of the American Chemical Society (American Chemical Society (ACS)). 1957, 79 (21): 5832–5832. ISSN 0002-7863. doi:10.1021/ja01578a073.
^ ^5.0 ^5.1 Brauer, Georg. Handbuch der präparativen anorganischen Chemie. Stuttgart: Enke. 1975: 278. ISBN 3-432-02328-6 （德語）.
^ Bartlett, N.; Lohmann, D. H. Two New Fluorides of Platinum. Proceedings of the Chemical Society (London). 1960: 14–15. doi:10.1039/PS9600000001.
^ Proceedings of the Chemical Society. June 1962. Proceedings of the Chemical Society (Royal Society of Chemistry (RSC)). 1962, (June): 218. ISSN 0369-8718. doi:10.1039/ps9620000197.
^ Bartlett, Neil; Lohmann, D. H. Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), [O
2]+
[PtF
6]−
.. J. Chem. Soc. 1962, 115: 5253–5261. doi:10.1039/jr9620005253.
^ Gulliver, D.J.; Levason, W. The chemistry of ruthenium, osmium, rhodium, iridium, palladium and platinum in the higher oxidation states. Coordination Chemistry Reviews (Elsevier BV). 1982, 46: 1–127. ISSN 0010-8545. doi:10.1016/0010-8545(82)85001-7.
^ ^10.0 ^10.1 Gortsema, F. P.; Toeniskoetter, R. H. The Chemistry of Platinum Hexafluoride. I. Reactions with Nitric Oxide, Dinitrogen Tetroxide, Nitrosyl Fluoride, and Nitryl Fluoride. Inorganic Chemistry (American Chemical Society (ACS)). 1966, 5 (7): 1217–1222. ISSN 0020-1669. doi:10.1021/ic50041a031.
^ Christe, Karl O. The hexafluorochlorine (VII) cation, CIF6+. Inorganic and Nuclear Chemistry Letters. 1972, 8 (8): 741–745. ISSN 0020-1650. doi:10.1016/0020-1650(72)80129-6.
^ US 3709748A,「Ionic interhalogen oxidizing agent and method」
^ Mazej, Z.; Goreshnik, E.; Christe, K.O. Photochemical preparation of Cs[MF6] salts (M = Ru, Rh, Os, Ir, Pt); crystal structures and Raman spectra. Journal of Fluorine Chemistry (Elsevier BV). 2023, 268: 110128. ISSN 0022-1139. doi:10.1016/j.jfluchem.2023.110128.

延伸閱讀

Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.

[Handbook-1] 1.0 ^1.1 ^1.2 ^1.3 Lide, David R. (編). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英語：CRC Press）. 2009: 4–81. ISBN 978-1-4200-9084-0 （英語）.

[:1-2] 2.0 ^2.1 ^2.2 ^2.3 Weinstock, Bernard; Malm, John G.; Weaver, E. Eugene. The Preparation and Some Properties of Platinum Hexafluoride. Journal of the American Chemical Society (American Chemical Society (ACS)). 1961, 83 (21): 4310–4317. ISSN 0002-7863. doi:10.1021/ja01482a002.

[Seppelt-3] 3.0 ^3.1 ^3.2 ^3.3 Drews, Thomas; Supeł, Joanna; Hagenbach, Adelheid; Seppelt, Konrad. Solid State Molecular Structures of Transition Metal Hexafluorides. Inorganic Chemistry (American Chemical Society (ACS)). 2006-03-28, 45 (9): 3782–3788. ISSN 0020-1669. doi:10.1021/ic052029f.

[4] Weinstock, Bernard; Claassen, Howard H.; Malm, John G. Platinum Hexafluoride. Journal of the American Chemical Society (American Chemical Society (ACS)). 1957, 79 (21): 5832–5832. ISSN 0002-7863. doi:10.1021/ja01578a073.

[:0-5] 5.0 ^5.1 Brauer, Georg. Handbuch der präparativen anorganischen Chemie. Stuttgart: Enke. 1975: 278. ISBN 3-432-02328-6 （德語）.

[6] Bartlett, N.; Lohmann, D. H. Two New Fluorides of Platinum. Proceedings of the Chemical Society (London). 1960: 14–15. doi:10.1039/PS9600000001.

[7] Proceedings of the Chemical Society. June 1962. Proceedings of the Chemical Society (Royal Society of Chemistry (RSC)). 1962, (June): 218. ISSN 0369-8718. doi:10.1039/ps9620000197.

[8] Bartlett, Neil; Lohmann, D. H. Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), [O
2]+
[PtF
6]−
.. J. Chem. Soc. 1962, 115: 5253–5261. doi:10.1039/jr9620005253.

[9] Gulliver, D.J.; Levason, W. The chemistry of ruthenium, osmium, rhodium, iridium, palladium and platinum in the higher oxidation states. Coordination Chemistry Reviews (Elsevier BV). 1982, 46: 1–127. ISSN 0010-8545. doi:10.1016/0010-8545(82)85001-7.

[:2-10] 10.0 ^10.1 Gortsema, F. P.; Toeniskoetter, R. H. The Chemistry of Platinum Hexafluoride. I. Reactions with Nitric Oxide, Dinitrogen Tetroxide, Nitrosyl Fluoride, and Nitryl Fluoride. Inorganic Chemistry (American Chemical Society (ACS)). 1966, 5 (7): 1217–1222. ISSN 0020-1669. doi:10.1021/ic50041a031.

[Christe-11] Christe, Karl O. The hexafluorochlorine (VII) cation, CIF6+. Inorganic and Nuclear Chemistry Letters. 1972, 8 (8): 741–745. ISSN 0020-1650. doi:10.1016/0020-1650(72)80129-6.

[12] US 3709748A,「Ionic interhalogen oxidizing agent and method」

[13] Mazej, Z.; Goreshnik, E.; Christe, K.O. Photochemical preparation of Cs[MF6] salts (M = Ru, Rh, Os, Ir, Pt); crystal structures and Raman spectra. Journal of Fluorine Chemistry (Elsevier BV). 2023, 268: 110128. ISSN 0022-1139. doi:10.1016/j.jfluchem.2023.110128.

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