六氟化铂

六氟化铂
	IUPAC名; Platinum hexafluoride
别名	氟化铂(VI)
识别
CAS号	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
性质
化学式	PtF6
摩尔质量	309.1 g·mol⁻¹
外观	暗红色易挥发性的固体; 蒸气为类似溴的红棕色
密度	5.21 g/cm3（计算）; 3.826 g/cm3（液态，64.3 °C）
熔点	61.3 °C
沸点	69.1 °C
溶解性（水）	水解
结构
晶体结构	正交晶系
空间群	Pnma (No. 62)
晶格常数	a = 937.4 pm, b = 852.7 pm, c = 493.3 pm
危险性
主要危害	氧化性
相关物质
相关化学品	六氟合铂酸氙
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

六氟化铂，又称氟化铂(VI)，化学式为Pt F₆。它是一个深红色的挥发性固体，气态时则变成红棕色。该化合物中铂的氧化态为+6，只有四个d电子，呈顺磁性，基态时为三线态。PtF₆是很强的氧化剂和氟化剂，甚至可以氧化氙，造就第一个惰性气体化合物六氟合铂酸氙的发现。

合成

PtF₆首次由金属铂与氟气化合制备，^[4]此反应至今仍是首选方法。^[3]

Pt + 3 F₂ → PtF₆

此外，六氟化铂也可由PtF₅在130 °C下歧化得到，^[5]而反应物PtF₅可由氟化PtCl₂制得。^[6]

2 PtCl₂ + 5 F₂ → 2 PtF₅ + 2 Cl₂

2 PtF₅ → PtF₆ + PtF₄

性质

六氟化铂是暗红色晶体，^[1]蒸汽则呈红棕色，在200 °C下仍然稳定。^[5]固态和气态六氟化铂都为八面体构型，Pt-F键长为185 pm。^[3]

反应

PtF₆是强氧化剂，甚至可以和氙反应，生成六氟合铂酸氙（XePtF₆）。1962年发现的此反应证明了惰性气体也能形成化合物。^[7]此外，PtF₆也可以氧化氧气，生成含有二氧基（O₂⁺）的化合物六氟合铂酸氧（O₂PtF₆）。^[8]它剧烈水解，生成[PtF₆]^2-，并放出氧气。^[9]

PtF₆能和三氟化溴、四氟化镎、四氟化钚反应，分别生成五氟化溴、六氟化镎、六氟化钚。^[2]它还能和亚硝酰氟、硝酰氟、四氧化二氮反应，分别生成NOPtF₆、NO₂PtF₆、N₂O₃PtF₆。^[10]PtF₆也会和一氧化氮反应，产生NOPtF₆，但无法和一氧化二氮反应。^[10]

它和氯酰氟^[11]或五氟化氯^[12]反应，生成六氟合氯(VII)𬭩盐。它和氟化铯在氟化氢里反应，生成CsPtF₆，并放出氟气。^[13]

参考资料

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

延伸阅读

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. (编). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英语：CRC Press）. 2009: 4–81. ISBN 978-1-4200-9084-0 （英语）.

[: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 （德语）.

[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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