Phosphorus pentasulfide

Phosphorus decasulfide
Names
	Other names phosphorus sulfide; sulfur phosphide; phosphorus persulfide; diphosphorus pentasulfide; tetraphosphorus decasulfide ; phosphorus decasulfide
Identifiers
CAS Number	1314-80-3 ;
3D model (JSmol)	Interactive image;
ChemSpider	14133 ;
ECHA InfoCard	100.013.858
EC Number	215-242-4;
PubChem CID	14817;
RTECS number	TH4375000;
UNII	HJ1X20J1DX ;
CompTox Dashboard (EPA)	DTXSID0051659 ;
	InChI InChI=1S/P4S10/c5-1-9-2(6)12-3(7,10-1)14-4(8,11-1)13-2 Key: CYQAYERJWZKYML-UHFFFAOYSA-N ; InChI=1/P4S10/c5-1-9-2(6)12-3(7,10-1)14-4(8,11-1)13-2 Key: CYQAYERJWZKYML-UHFFFAOYAD;
	SMILES P12(=S)SP3(=S)SP(=S)(S1)SP(=S)(S2)S3;
Properties
Chemical formula	P2S5 or dimer P4S10
Molar mass	222.27 g mol
Appearance	greenish-gray to yellow solid[1]
Odor	rotten eggs[1]
Density	2.09 g/cm3
Melting point	288 °C (550 °F; 561 K)
Boiling point	514 °C (957 °F; 787 K)
Solubility in water	hydrolyses
Solubility in other solvents	0.222 g / 100g CS2 (at 17 °C); Insoluble in C6H6; Insoluble in hot xylene; Insoluble in hot anisole.
Vapor pressure	1 mmHg (300°C)[1]
Structure
Crystal structure	triclinic, aP28
Space group	P-1, No. 2
Point group	Td
Hazards
	Lethal dose or concentration (LD, LC):
LD50 (median dose)	389 mg/kg (oral, rat)[2]
	NIOSH (US health exposure limits):
PEL (Permissible)	TWA 1 mg/m3[1]
REL (Recommended)	TWA 1 mg/m3 ST 3 mg/m3[1]
IDLH (Immediate danger)	250 mg/m3[1]
Related compounds
Related compounds	P4S3
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

Phosphorus pentasulfide is the inorganic compound with the formula P₂S₅ or dimer P₄S₁₀. This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.[3]

Structure and synthesis

Its tetrahedral molecular structure is similar to that of adamantane and almost identical to the structure of phosphorus pentoxide.[4]

Phosphorus pentasulfide is obtained by the reaction of liquid white phosphorus (P₄) with sulfur above 300 °C. The first synthesis of P₄S₁₀ by Berzelius in 1843 [5][6] was by this method. Alternatively, P₄S₁₀ can be formed by reacting elemental sulfur or pyrite, FeS₂, with ferrophosphorus, a crude form of Fe₂P (a byproduct of P₄ production from phosphate rock):

4 Fe₂P + 18 S → P₄S₁₀ + 8 FeS

4 Fe₂P + 18 FeS₂ + heat → P₄S₁₀ + 26 FeS

Applications

Approximately 150,000 tons of P₄S₁₀ are produced annually. The compound is mainly converted to other derivatives for use as lubrication additives such zinc dithiophosphates. It is also used in the production of pesticides such as Parathion and Malathion.[7] It is also a component of some amorphous solid electrolytes (e.g. Li₂S-P₂S₅) for some types of lithium batteries.

Phosphorus pentasulfide is a dual-use material, for the production of early insecticides such as Amiton and also for the manufacture of the related VX nerve agents.

Reactivity

Due to hydrolysis by atmospheric moisture, P₄S₁₀ evolves H₂S, thus P₄S₁₀ is associated with a rotten egg odour. Aside from H₂S, hydrolysis of P₄S₁₀ eventually gives phosphoric acid:

P₄S₁₀ + 16 H₂O → 4 H₃PO₄ + 10 H₂S

Other mild nucleophiles react with P₄S₁₀, including alcohols and amines. Aromatic compounds such as anisole, ferrocene and 1-methoxynaphthalene react to form 1,3,2,4-dithiadiphosphetane 2,4-disulfides such as Lawesson's reagent.

P₄S₁₀ is used as a thionation reagent. Reactions of this type require refluxing solvents such as benzene, dioxane, or acetonitrile with P₄S₁₀ dissociating into P₂S₅. Some ketones, esters, and imides are converted to the corresponding thiocarbonyls. Amides give thioamide. With 1,4-diketones the reagent forms thiophenes. It is also used to deoxygenate sulfoxides. The use of P₄S₁₀ has been displaced by Lawesson's reagent P₄S₁₀s.[8]

P₂S₅ reacts with pyridine to form the complex P₂S₅(pyridine)₂.[9]

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References

NIOSH Pocket Guide to Chemical Hazards. "#0510". National Institute for Occupational Safety and Health (NIOSH).
"Phosphorus pentasulfide". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
Scott D. Edmondson, Mousumi Sannigrahi "Phosphorus(V) sulfide" Encyclopedia of Reagents for Organic Synthesis 2004 John Wiley & Sons. doi:10.1002/047084289X.rp166s.pub2
Corbridge, D. E. C. (1995). Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam: Elsevier. ISBN 0-444-89307-5.
Berzelius, J. (1843). "Ueber die Verbindungen des Phosphors mit Schwefel". Annalen der Chemie und Pharmacie. 46 (2): 129–154. doi:10.1002/jlac.18430460202.
Berzelius, J. (1843). "Ueber die Verbindungen des Phosphors mit Schwefel". Annalen der Chemie und Pharmacie. 46 (3): 251–281. doi:10.1002/jlac.18430460303. (continuation of p. 154 of the same volume)
Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. (2002). "Phosphorus Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730.
Ozturk, T.; Ertas, E.; Mert, O. (2010). "A Berzelius Reagent, Phosphorus Decasulfide (P₄S₁₀), in Organic Syntheses". Chemical Reviews. 110 (6): 3419–3478. doi:10.1021/cr900243d. PMID 20429553.
Bergman, Jan; Pettersson, Birgitta; Hasimbegovic, Vedran; Svensson, Per H. (2011). "Thionations Using a P4S10−Pyridine Complex in Solvents Such as Acetonitrile and Dimethyl Sulfone". The Journal of Organic Chemistry. 76 (6): 1546–1553. doi:10.1021/jo101865y. PMID 21341727.

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[PGCH-1] NIOSH Pocket Guide to Chemical Hazards. "#0510". National Institute for Occupational Safety and Health (NIOSH).

[2] "Phosphorus pentasulfide". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).

[3] Scott D. Edmondson, Mousumi Sannigrahi "Phosphorus(V) sulfide" Encyclopedia of Reagents for Organic Synthesis 2004 John Wiley & Sons. doi:10.1002/047084289X.rp166s.pub2

[4] Corbridge, D. E. C. (1995). Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam: Elsevier. ISBN 0-444-89307-5.

[5] Berzelius, J. (1843). "Ueber die Verbindungen des Phosphors mit Schwefel". Annalen der Chemie und Pharmacie. 46 (2): 129–154. doi:10.1002/jlac.18430460202.

[6] Berzelius, J. (1843). "Ueber die Verbindungen des Phosphors mit Schwefel". Annalen der Chemie und Pharmacie. 46 (3): 251–281. doi:10.1002/jlac.18430460303. (continuation of p. 154 of the same volume)

[7] Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. (2002). "Phosphorus Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730.

[8] Ozturk, T.; Ertas, E.; Mert, O. (2010). "A Berzelius Reagent, Phosphorus Decasulfide (P₄S₁₀), in Organic Syntheses". Chemical Reviews. 110 (6): 3419–3478. doi:10.1021/cr900243d. PMID 20429553.

[9] Bergman, Jan; Pettersson, Birgitta; Hasimbegovic, Vedran; Svensson, Per H. (2011). "Thionations Using a P4S10−Pyridine Complex in Solvents Such as Acetonitrile and Dimethyl Sulfone". The Journal of Organic Chemistry. 76 (6): 1546–1553. doi:10.1021/jo101865y. PMID 21341727.