Phosphine (IUPAC name: phosphane) is the compound with the chemical formula PH3. It is a colorless, flammable, toxic gas. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like garlic or rotting fish, due to the presence of substituted phosphine and diphosphane (P2H4). With traces of P2H4 present, PH3 is spontaneously flammable in air, burning with a luminous flame. Phosphines are also a group of organophosphorus compounds with the formula R3P (R = organic derivative). Organophosphines are important in catalysts where they complex to various metal ions; complexes derived from a chiral phosphine can catalyze reactions to give chiral, enantioenriched products.
History
Philippe Gengembre (1764-1838), a student of Lavoisier, first obtained phosphine in 1783 by heating phosphorus in an aqueous solution of potash (potassium carbonate).
Perhaps because of its strong association with elemental phosphorus, phosphine was once regarded as a gaseous form of the element, but Lavoisier (1789) recognised it as a combination of phosphorus with hydrogen and described it as phosphure d'hydrogène (phosphide of hydrogen).
In 1844, Paul Thénard, son of the French chemist Louis Jacques Thénard, used a cold trap to separate diphosphine from phosphine that had been generated from calcium phosphide, thereby demonstrating that P2H4 is responsible for spontaneous flammability associated with PH3, and also for the characteristic orange/brown color that can form on surfaces, which is a polymerisation product. He considered diphosphine’s formula to be PH2, and thus an intermediate between elemental phosphorus, the higher polymers, and phosphine. Calcium phosphide (nominally Ca3P2) produces more P2H4 than other phosphides because of the preponderance of P-P bonds in the starting material.
The name "phosphine" first appeared in combined form in 1857. The gas PH3 was named "phosphine" by 1865 (or earlier).
Structure and properties
PH3 is a trigonal pyramidal molecule with C3v molecular symmetry. The length of the P-H bond is 1.42 Ã…, the H-P-H bond angles are 93.5°. The dipole moment is 0.58 D, which increases with substitution of methyl groups in the series: CH3PH2, 1.10 D; (CH3)2PH, 1.23 D; (CH3)3P, 1.19 D. In contrast, the dipole moments of amines decrease with substitution, starting with ammonia, which has a dipole moment of 1.47 D. The low dipole moment and almost orthogonal bond angles lead to the conclusion that in PH3 the P-H bonds are almost entirely pσ(P) â€" sσ(H) and phosphorus 3s orbital contributes little to the bonding between phosphorus and hydrogen in this molecule. For this reason, the lone pair on phosphorus may be regarded as predominantly formed by the 3s orbital of phosphorus. The upfield chemical shift of the phosphorus atom in the 31P NMR spectrum accords with the conclusion that the lone pair electrons occupy the 3s orbital (Fluck, 1973). This electronic structure leads to a lack of nucleophilicity and an ability to form only weak hydrogen bonds.
The aqueous solubility of PH3 is slight; 0.22 mL of gas dissolve in 1 mL of water. Phosphine dissolves more readily in non-polar solvents than in water because of the non-polar P-H bonds. It acts as neither an acid nor a base in water. Proton exchange proceeds via a phosphonium (PH4+) ion in acidic solutions and via PH2âˆ' at high pH, with equilibrium constants Kb = 4 × 10âˆ'28 and Kz = 41.6 × 10âˆ'29.
Phosphine burns producing a dense white cloud of phosphorus pentoxide:
- 2 PH3 + 4 O2 â†' P2O5 + 3 H2O
Preparation and occurrence
Phosphine may be prepared in a variety of ways. Industrially it can be made by the reaction of white phosphorus with sodium or potassium hydroxide, producing sodium or potassium hypophosphite as a by-product.
- 3KOH + P4 + 3H2O â†' 3KH2PO2 + PH3
Alternatively the acid-catalyzed disproportioning of white phosphorus may be used, which yields phosphoric acid and phosphine. Both routes have industrial significance; the acid route is preferred method if further reaction of the phosphine to substituted phosphines is needed. The acid route requires purification and pressurizing. It can also be made (as described above) by the hydrolysis of a metal phosphide, such as aluminium phosphide or calcium phosphide. Pure samples of phosphine, free from P2H4, may be prepared using the action of potassium hydroxide on phosphonium iodide (PH4I).
Phosphine is a constituent of the atmosphere at very low and highly variable concentrations. It may contribute significantly to the global phosphorus biochemical cycle. The most likely source is reduction of phosphate in decaying organic matter, possibly via partial reductions and disproportionations, since environmental systems do not have known reducing agents of sufficient strength to directly convert phosphate to phosphine .
Phosphines
Related to a PH3 is the class of organophosphorus compounds commonly called phosphines. These alkyl and aryl derivatives of phosphine are analogous to organic amines. Common examples include triphenylphosphine ((C6H5)3P) and BINAP, both used as ligands in homogeneous catalysis or triisopropylphosphine. Phosphines are easily oxidized to phosphine oxides as exemplified by the directed synthesis of a phospha-crown, the phosphorus analogue of an aza crown where it is not possible to isolate the phosphine itself.
In step 1 diphosphinoethane coordinates to a ferrocene containing additional carbon monoxide ligands and an acetonitrile ligand. The next step is a hydrophosphination with trivinylphosphine followed by alkylation with ethyl bromide and hydrogenation with hydrogen over palladium on carbon. In the final step the iron template is removed by bromine but oxidation of the phosphine groups is unavoidable.
When modified with suitable substituents as in certain (rare) diazaphospholenes (scheme 3) the polarity of the P-H bond can be inverted (see: umpolung) and the resulting phosphine hydride can reduce a carbonyl group as in the example of benzophenone in yet another way.
Applications
Organophosphorus chemistry
Phosphine is mainly consumed as an intermediate in organophosphorus chemistry. In an illustrative reaction, formaldehyde adds in the presence of hydrogen chloride to give tetrakis(hydroxymethyl)phosphonium chloride, which is used in textiles.
Microelectronics
Small amounts of phosphine are used as a dopant in the semiconductor industry, and a precursor for the deposition of compound semiconductors.
Fumigant
For farm use, pellets of aluminium phosphide, calcium phosphide, or zinc phosphide release phosphine upon contact with atmospheric water or rodents' stomach acid. These pellets also contain agents to reduce the potential for ignition or explosion of the released phosphine.
Because the previously popular fumigant methyl bromide has been phased out in some countries under the Montreal Protocol, phosphine is the only widely used, cost-effective, rapidly acting fumigant that does not leave residues on the stored product. Pests with high levels of resistance toward phosphine have become common in Asia, Australia and Brazil. High level resistance is also likely to occur in other regions, but has not been as closely monitored. Genetic variants that contribute to high level resistance to phosphine have been identified in the dihydrolipoamide dehydrogenase gene. Identification of this gene now allows rapid molecular identification of resistant insects.
Safety
Phosphine gas is more dense than air and hence may collect in low-lying areas. It can form explosive mixtures with air and also self-ignite.
Phosphine can be absorbed into the body by inhalation. Direct contact with phosphine liquid â€" although unlikely to occur â€" may cause frostbite, like other cryogenic liquids. The main target organ of phosphine gas is the respiratory tract. According to the 2009 U.S. National Institute for Occupational Safety and Health (NIOSH) pocket guide, and U.S. Occupational Safety and Health Administration (OSHA) regulation, the 8 hour average respiratory exposure should not exceed 0.3 ppm. NIOSH recommends that the short term respiratory exposure to phosphine gas should not exceed 1 ppm. The Immediately Dangerous to Life or Health level is 50 ppm. Overexposure to phosphine gas causes nausea, vomiting, abdominal pain, diarrhea; thirst; chest tightness, dyspnea (breathing difficulty); muscle pain, chills; stupor or syncope; pulmonary edema. Phosphine has been reported to have the odor of decaying fish or garlic at concentrations below 0.3 ppm. The smell is normally restricted to laboratory areas or phosphine processing since the smell comes from the way the phosphine is extracted from the environment. However, it may occur elsewhere, such as in industrial waste landfills. Exposure to higher concentrations may cause olfactory fatigue.
Deaths have resulted from accidental exposure to fumigation materials containing aluminum phosphide or phosphine.
See also
- Diphosphane, H2PPH2, simplified to H4P2
- Diphosphines, R2PPR2, R2P(CH2)nPR2
- Diphosphene, HP=PH
- Diphosphenes, R-P=P-R'
- Phosphine oxide, R3P=O
- Phosphorane, PR5, R3P=CR2
- Phosphinite, P(OR)R2
- Phosphonite, P(OR)2R
- Phosphite, P(OR)3
- Phosphinate, R2P(RO)O
- Phosphonate, RP(RO)2O
- Phosphate, P(RO)3O
References
Further reading
- Fluck, E. (1973). "The Chemistry of Phosphine". Topics in Current Chemistry. Fortschritte der Chemischen Forschung 35: 1â€"64. doi:10.1007/BFb0051358. ISBN 3-540-06080-4.Â
- WHO (World Health Organisation) (1988). Phosphine and Selected Metal Phosphides. Environmental Health Criteria 73. Geneva: Joint sponsorship of UNEP, ILO and WHO.Â
External links
- International Chemical Safety Card 0694
- CDC - Phosphine - NIOSH Workplace Safety and Health Topic