Phosphine (IUPAC name: phosphane) is the compound with the chemical formula PH3. It is a colorless, flammable, toxic gas and pnictogen hydride. 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.

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).

PH3 is a trigonal pyramidal molecule with C3v molecular symmetry. The length of the P-H bond is 1.42 Å, 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) – 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.

This page was last edited on 10 April 2018, at 10:03.
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