There are several other phosphorus sulfides in addition to P4S3 and P4S10. Six of these phosphorus sulfides exist as isomers: P4S4, P4S5, P4S6, P4S7, P4S8, and P4S9. These isomers are distinguished by Greek letter prefixes. The prefix is based on the order of the discovery of the isomers, not their structure.[1] All known molecular phosphorus sulfides contain a tetrahedral array of four phosphorus atoms.[2]P4S2 is also known but is unstable above −30 °C.[3]
The main method for preparing these compounds is thermolysis of mixtures of phosphorus and sulfur. The product distributions can be analyzed by 31P-NMR spectroscopy. More selective syntheses entail:
Phosphorus sesquisulfide is prepared by treating red phosphorus with sulfur above 450 K,[6] followed by careful recrystallization with carbon disulfide and benzene. An alternative method involves the controlled fusion of white phosphorus with sulfur in an inert, non-flammable solvent.[7]
P4S5 can be prepared by treating stoichiometric amounts of P4S3 with sulfur in carbon disulfide solution, in the presence of light and a catalytic amount of iodine.[8] The respective product distribution is then analyzed by using 31P-NMR spectroscopy.
In particular, α-P4S5 can be easily made by the photochemical reactionofP4S10 with red phosphorus.[6] Note that P4S5 is unstable when heated, tending to disproportionatetoP4S3 and P4S7 before reaching its melting point.[9]
P4S9 can be made by two methods. One method involves the heating of P4S3 in excess sulfur.[6] Another
method involves the heating of P4S7 and P4S10 in 1:2 mole ratio, where P4S9 is reversibly formed:[10]
P4S10 is one of the most stable phosphorus sulfides. It is most easily made by heating white phosphorus with sulfur above 570 K in an evacuated tube.[12]
^Jason, M. E.; Ngo, T.; Rahman, S. (1997). "Products and Mechanisms in the Oxidation of Phosphorus by Sulfur at Low Temperature". Inorg. Chem.36 (12): 2633–2640. doi:10.1021/ic9614879.
^Holleman, A. F.; Wiberg, E. Inorganic Chemistry. Academic Press: San Diego, 2001. ISBN0-12-352651-5.
^Heal, H. G. The Inorganic Heterocyclic Chemistry of Sulfur, Nitrogen, and Phosphorus Academic Press: London; 1980 ISBN0-12-335680-6.
^ abcJason, M. E. (1997). "Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P4Sn Species". Inorg. Chem.36 (12): 2641–2646. doi:10.1021/ic9614881.
^ abcdeCatherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 15: The group 15 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 484. ISBN978-0-13-175553-6.
^"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 (2002). "Phosphorus". Chemistry of the elements, 2nd edition. Butterworth Heinemann. p. 508. ISBN0750633654.
^ abR. Bruce King (2005). "Phosphorus". Encyclopedia of Inorganic Chemistry, 2nd edition. Wiley. p. 3711. ISBN9780470862100.
^"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.