Phosphorus sulfides
Template:Short description Phosphorus sulfides comprise a family of inorganic compounds containing only phosphorus and sulfur. These compounds have the formula Template:Chem2 with n ≤ 10. Two are of commercial significance, phosphorus pentasulfide (Template:Chem2), which is made on a kiloton scale for the production of other organosulfur compounds, and phosphorus sesquisulfide (Template:Chem2), used in the production of "strike anywhere matches".
There are several other phosphorus sulfides in addition to Template:Chem2 and Template:Chem2. Six of these phosphorus sulfides exist as isomers: Template:Chem2. 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] Template:Chem2 is also known but is unstable above −30 °C.[3]
Phosphorus monosulfide monomer, PS, is highly unstable and only exists at elevated temperatures. Its bond, worth about 55 kcal/mol, is about 2.4 angstroms long.[4]
Preparation
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:
- desulfurization, e.g. using triphenylphosphine and, complementarily,
- sulfidation using triphenylarsine sulfide.[5][6]
Template:Chem2
Phosphorus sesquisulfide is prepared by treating red phosphorus with sulfur above 450 K,[7] 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.[8]
Template:Chem2
The α- and β- forms of Template:Chem2 can be prepared by treating the corresponding isomers of Template:Chem2 with Template:Chem2:[7]
Template:Chem2 can be synthesized by the reaction of stoichiometric amounts of phosphorus, sulfur, and iodine.
Template:Chem2
Template:Chem2 can be prepared by treating stoichiometric amounts of Template:Chem2 with sulfur in carbon disulfide solution, in the presence of light and a catalytic amount of iodine.[9] The respective product distribution is then analyzed by using 31P-NMR spectroscopy.
In particular, α-Template:Chem2 can be easily made by the photochemical reaction of Template:Chem2 with red phosphorus.[7] Note that Template:Chem2 is unstable when heated, tending to disproportionate to Template:Chem2 and Template:Chem2 before reaching its melting point.[10]
Template:Chem2
Template:Chem2 can be made by abstracting a sulfur atom from Template:Chem2 using triphenylphosphine:[7]
Treating α-Template:Chem2 with Template:Chem2 in Template:Chem2 also yields α-Template:Chem2.[5] The two new polymorphs δ-Template:Chem2 and ε-Template:Chem2 can be made by treating α-Template:Chem2 with Template:Chem2 in Template:Chem2.[11]
Template:Chem2
Template:Chem2 is most conveniently made by direct union of the corresponding elements, and is one of the most easily purified binary phosphorus sulfides.[12]
Template:Chem2
β-Template:Chem2 can be made by treating α-Template:Chem2 with Template:Chem2 in Template:Chem2, which yields a mixture between α-Template:Chem2 and β-Template:Chem2.[5]
Template:Chem2
Template:Chem2 can be made by two methods. One method involves the heating of Template:Chem2 in excess sulfur.[7] Another method involves the heating of Template:Chem2 and Template:Chem2 in 1:2 mole ratio, where Template:Chem2 is reversibly formed:[11]
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[[Phosphorus pentasulfide|Template:Chem2]] 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.[13]
See also
References
- ↑ Script error: No such module "Citation/CS1".
- ↑ Holleman, A. F.; Wiberg, E. Inorganic Chemistry. Academic Press: San Diego, 2001. Template:ISBN.
- ↑ Heal, H. G. The Inorganic Heterocyclic Chemistry of Sulfur, Nitrogen, and Phosphorus Academic Press: London; 1980 Template:ISBN.
- ↑ Script error: No such module "citation/CS1".
- ↑ a b c Script error: No such module "Citation/CS1".
- ↑ Script error: No such module "Citation/CS1".
- ↑ a b c d e Script error: No such module "citation/CS1".
- ↑ "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.
- ↑ Script error: No such module "citation/CS1".
- ↑ a b Script error: No such module "citation/CS1".
- ↑ "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.