Pyramidal inversion

In chemistry, pyramidal inversion (also umbrella inversion) is a fluxional process in compounds with a pyramidal molecule, such as ammonia (NH3) "turns inside out". It is a rapid oscillation of the atom and substituents, the molecule or ion passing through a planar transition state. For a compound that would otherwise be chiral due to a stereocenter, pyramidal inversion allows its enantiomers to racemize. The general phenomenon of pyramidal inversion applies to many types of molecules, including carbanions, amines, phosphines, arsines, stibines, and sulfoxides. The identity of the inverting atom has a dominating influence on the barrier. Inversion of ammonia is rapid at room temperature. In contrast, phosphine (PH3) inverts very slowly at room temperature (energy barrier: 132 kJ/mol). Consequently, amines of the type RR′R"N usually are not optically stable (enantiomers racemize rapidly at room temperature), but P-chiral phosphines are. Appropriately substituted sulfonium salts, sulfoxides, arsines, etc. are also optically stable near room temperature. Steric effects can also influence the barrier. The ammonia interconversion is rapid at room temperature, inverting 30 billion times per second. Two factors contribute to the rapidity of the inversion: a low energy barrier (24.2 kJ/mol; 5.8 kcal/mol) and a narrow width of the barrier itself, which allows for frequent quantum tunnelling (see below). In contrast, phosphine (PH3) inverts very slowly at room temperature (energy barrier: 132 kJ/mol). Pyramidal inversion in nitrogen and amines is known as nitrogen inversion. It is a rapid oscillation of the nitrogen atom and substituents, the nitrogen "moving" through the plane formed by the substituents (although the substituents also move - in the other direction); the molecule passing through a planar transition state. For a compound that would otherwise be chiral due to a nitrogen stereocenter, nitrogen inversion provides a low energy pathway for racemization, usually making chiral resolution impossible.