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磷的硫化物是一类无机化合物，只由磷和硫组成，通式为 P₄S_x（x ≤ 10）。其中两种磷的硫化物具有商业意义：十硫化四磷 (P₄S₁₀)的产量达到千吨规模，用于生产有机硫化合物；而三硫化四磷 (P₄S₃)可用于制造火柴。

除了 P₄S₃ 和P₄S₁₀以外，还存在多种磷的硫化物。其中六种有异构体：P₄S₄、P₄S₅、P₄S₆、P₄S₇、P₄S₈和 P₄S₉。它们的异构体以希腊字母前缀区别。这些前缀是以发现顺序排列的，而不是结构。^[1] 所有已知的磷的硫化物分子的四个磷原子都为四面体型排列（类似白磷）。^[2] P₄S₂ 也是已知的，不过在 −30 °C以上不稳定。^[3]

制备

磷的硫化物的主要制备方法是加热磷和硫的混合物。产物可以由 ³¹P 核磁共振波谱法分析。更具选择性的合成需要用三苯基膦脱硫，或是用硫化三苯基胂硫化。^[4]^[5]

P₄S₃

三硫化四磷可以由红磷和硫在 450 K以上反应，^[6] 然后用二硫化碳和苯小心地重结晶。另一种制备方法是将白磷和硫在惰性、不易燃的溶剂里反应而成。^[7]

P₄S₄

α型和β型的 P₄S₄可以由 P₄S₃I₂ 的对应异构体和((CH₃)₃Sn)₂S 反应而成：^[6]

反应前体 P₄S₃I₂ 则可以由化学计量的磷、硫和碘反应而成。

P₄S₅

P₄S₅ 可以由化学计量的 P₄S₃ 和硫的二硫化碳溶液在光照和催化量的碘下反应而成。^[8]产物可以通过使用磷-31核磁共振波谱法（英语：31P NMR spectroscopy）分析。

α-P₄S₅ 可以通过 P₄S₁₀和红磷的光化学反应而成。^[6] P₄S₅ 是对热不稳定的，会在达到熔点之前歧化成 P₄S₃ 和 P₄S₇。^[9]

P₄S₆

P₄S₆ 可以由 P₄S₇ 被三苯基膦夺走一个硫原子而成：^[6]

P₄S₇ + Ph₃P → P₄S₆ + Ph₃PS

α-P₄S₅ 和溶于二硫化碳的Ph₃AsS 反应，也可以得到 α-P₄S₆。^[4]两种新的六硫化四磷异构体δ-P₄S₆ 和ε-P₄S₆可以由 α-P₄S₄ 和溶于二硫化碳的Ph₃SbS 反应而成。^[10]

P₄S₇

P₄S₇ 可以由磷和硫直接反应而成，是最容易提纯的磷的硫化物之一。^[11]

4 P + 7 S → P₄S₇

P₄S₈

β-P₄S₈可以由 α-P₄S₇ 和溶于二硫化碳的 Ph₃AsS 反应而成，会产生α-P₄S₇ 和β-P₄S₈的混合物。^[4]

P₄S₉

P₄S₉ 的制备有两种方法。一种方法是 P₄S₃和过量的硫加热反应而成。^[6]

另一种方法则是以1:2 的比例混合P₄S₇ 和 P₄S₁₀，会产生 P₄S₉。这个反应为可逆反应：^[10]

P₄S₇ + 2 P₄S₁₀ ⇌ 3 P₄S₉

P₄S₁₀

P₄S₁₀是最稳定的磷的硫化物之一。它可以通过在真空管中，将白磷和硫加热到 570 K 以上而成。^[12]

P₄ + 10 S → P₄S₁₀

参考资料

^ Jason, M. E.; Ngo, T.; Rahman, S. Products and Mechanisms in the Oxidation of Phosphorus by Sulfur at Low Temperature. Inorg. Chem. 1997, 36 (12): 2633–2640. doi:10.1021/ic9614879.
^ Holleman, A. F.; Wiberg, E. Inorganic Chemistry. Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
^ Heal, H. G. The Inorganic Heterocyclic Chemistry of Sulfur, Nitrogen, and Phosphorus Academic Press: London; 1980 ISBN 0-12-335680-6.
^ ^4.0 ^4.1 ^4.2 Jason, M. E. Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P₄S_n Species. Inorg. Chem. 1997, 36 (12): 2641–2646. doi:10.1021/ic9614881.
^ Nowottnick, H.; Blachnik, R. Zwei neue Phosphorsulfide (Two New Phosphorus Sulfides). Zeitschrift für anorganische und allgemeine Chemie. 1999, 625 (12): 1966–1968. doi:10.1002/(SICI)1521-3749(199912)625:12<1966::AID-ZAAC1966>3.0.CO;2-B.
^ ^6.0 ^6.1 ^6.2 ^6.3 ^6.4 Catherine E. Housecroft; Alan G. Sharpe. Chapter 15: The group 15 elements. Inorganic Chemistry, 3rd Edition. Pearson. 2008: 484. ISBN 978-0-13-175553-6.
^ "Phosphorus trisulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 563.
^ "Phosphorus pentasulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 565.
^ A. Earnshaw; Norman Greenwood. Phosphorus. Chemistry of the elements, 2nd edition. Butterworth Heinemann. 2002: 508. ISBN 0750633654.
^ ^10.0 ^10.1 R. Bruce King. Phosphorus. Encyclopedia of Inorganic Chemistry, 2nd edition. Wiley. 2005: 3711. ISBN 9780470862100.
^ "Phosphorus heptasulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 566.
^ "Diphosphorus pentasulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 567.

[1] Jason, M. E.; Ngo, T.; Rahman, S. Products and Mechanisms in the Oxidation of Phosphorus by Sulfur at Low Temperature. Inorg. Chem. 1997, 36 (12): 2633–2640. doi:10.1021/ic9614879.

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

[3] Heal, H. G. The Inorganic Heterocyclic Chemistry of Sulfur, Nitrogen, and Phosphorus Academic Press: London; 1980 ISBN 0-12-335680-6.

[Jason-4] 4.0 ^4.1 ^4.2 Jason, M. E. Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P₄S_n Species. Inorg. Chem. 1997, 36 (12): 2641–2646. doi:10.1021/ic9614881.

[5] Nowottnick, H.; Blachnik, R. Zwei neue Phosphorsulfide (Two New Phosphorus Sulfides). Zeitschrift für anorganische und allgemeine Chemie. 1999, 625 (12): 1966–1968. doi:10.1002/(SICI)1521-3749(199912)625:12<1966::AID-ZAAC1966>3.0.CO;2-B.

[InorgChem-6] 6.0 ^6.1 ^6.2 ^6.3 ^6.4 Catherine E. Housecroft; Alan G. Sharpe. Chapter 15: The group 15 elements. Inorganic Chemistry, 3rd Edition. Pearson. 2008: 484. ISBN 978-0-13-175553-6.

[7] "Phosphorus trisulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 563.

[8] "Phosphorus pentasulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 565.

[Elements-9] A. Earnshaw; Norman Greenwood. Phosphorus. Chemistry of the elements, 2nd edition. Butterworth Heinemann. 2002: 508. ISBN 0750633654.

[Encyclo-10] 10.0 ^10.1 R. Bruce King. Phosphorus. Encyclopedia of Inorganic Chemistry, 2nd edition. Wiley. 2005: 3711. ISBN 9780470862100.

[11] "Phosphorus heptasulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 566.

[12] "Diphosphorus pentasulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 567.

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磷的硫化物

制备

P₄S₃

P₄S₄

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P₄S₈

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