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.

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