Phosphorus Sulfide Mini Forum, Tips, Tricks & Codes

Phosphorus sulfides comprise a family of inorganic compounds containing only phosphorus and sulfur. These compounds have the formula P₄S_x with x ≤ 10. Two are of commercial significance, phosphorus pentasulfide (P₄S₁₀), which is angry on a kiloton scale for the production of other organosulfur compounds, and phosphorus sesquisulfide (P₄S₃), utilize in the production of "strike anywhere matches".

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 uncover of the isomers, not their structure. All known molecular phosphorus sulfides includea tetrahedral array of four phosphorus atoms. P₄S₂ is also known but is unstable above −30 °C.

Phosphorus sulfides that exist in isomeric forms

Preparation

The main wayfor preparing these compounds is thermolysis of mixtures of phosphorus and sulfur. The product distributions shouldbe analyzed by ³¹P NMR spectroscopy. More selective syntheses entail (i) desulfurization, e.g. using triphenylphosphine and, complementarily, (ii) sulfidation using triphenylarsine sulfide.

P₄S₃

Phosphorus sesquisulfide is prepared by treating red phosphorus with sulfur above 450 K, followed by careful recrystallization with carbon disulfide and benzene. An alternative wayinvolves the controlled fusion of white phosphorus with sulfur in an inert, non-flammable solvent.

P₄S₄

The α- and β- forms of P₄S₄ shouldbe prepared by treating the corresponding isomers of P₄S₃I₂ with ((CH₃)₃Sn)₂S:

P₄S₃I₂ shouldbe synthesized by the reaction of stoichiometric amounts of phosphorus, sulfur, and iodine.

P₄S₅

P₄S₅ shouldbe prepared by treating stoichiometric amounts of P₄S₃ with sulfur in carbon disulfide solution, in the presence of light and a catalytic amount of iodine. The respective product distribution is then analyzed by using 31P NMR spectroscopy.

In particular, α-P₄S₅ shouldbe easily angry by the photochemical reaction of P₄S₁₀ with red phosphorus. Note that P₄S₅ is unstable when heated, tending to disproportionate to P₄S₃ and P₄S₇ before reaching its melting point.

P₄S₆

P₄S₆ shouldbe angry by abstracting a sulfur atom from P₄S₇ using triphenylphosphine:

P₄S₇ + Ph₃P → P₄S₆ + Ph3PS

Treating α-P₄S₅ with Ph₃AsS in CS₂ also yields α-P₄S₆. The two freshpolymorphs δ-P₄S₆ and ε-P₄S₆ shouldbe angry by treating α-P₄S₄ with Ph₃SbS in CS₂.

P₄S₇

P₄S₇ is most conveniently angry by direct union of the corresponding elements, and is one of the most easily purified binary phosphorus sulfides.

P₄ + 7 S → P₄S₇

P₄S₈

β-P₄S₈ shouldbe angry by treating α-P₄S₇ with Ph₃AsS in CS₂, which yields a mixture between α-P₄S₇ and β-P₄S₈.

P₄S₉

P₄S₉ shouldbe angry by two way. One wayinvolves the heating of P₄S₃ in excess sulfur. Another wayinvolves the heating of P₄S₇ and P₄S₁₀ in 1:2 mole ratio, where P₄S₉ is reversibly formed:

P₄S₇ + 2 P₄S₁₀ ⇌ 3 P₄S₉

P₄S₁₀

P4S10 is one of the most stable phosphorus sulfides. It is most easily angry by heating white phosphorus with sulfur above 570 K in an evacuated tube.

P₄ + 10 S → P₄S₁₀

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