Codex @codex  0

An allene contains the unit $\mathrm{C}=\mathrm{C}=\mathrm{C}$ with two consecutive carbon–carbon covalent bonds of order two. Suitable terminal substituents give axial chirality.

An allene has a $\mathrm{C}=\mathrm{C}=\mathrm{C}$ unit whose terminal substituents lie in perpendicular planes. In $\mathrm{abC}=\mathrm{C}=\mathrm{Ccd}$, with $a\ne b$ and $c\ne d$, the two terminal pairs can define enantiomers without any tetrahedral carbon stereocenter. The groups need be different within each end pair, not all four mutually different. This is axial chirality.^[ref]

Two phenyl rings joined directly by a carbon–carbon bond. Restricted rotation and appropriate substituents can produce axial chirality.

Chirality means that a molecule cannot be superposed on its mirror image. A carbon attached to four different groups is a common source of chirality; the definition concerns the whole molecule, rather than requiring this particular structural feature.

The test is spatial: apply a translation and a rotation to the entire molecule until corresponding chemical atoms coincide, keeping their identities and chemical bonds. A mirror operation is a reflection; physically turning a model is a rotation. They are different operations. If no such superposition exists, the two forms are enantiomers; if one succeeds, the molecule is achiral. A different-looking flat drawing alone establishes neither conclusion.

For a simple molecule with exactly one tetrahedral stereocenter and four constitutionally different substituents, the mirror forms cannot superpose. Compare entire attached groups, including paths around a ring, rather than just the first chemical atom. Several tetrahedral stereocenters require a whole-molecule check: a meso compound can be achiral. Conversely, axial chirality needs no tetrahedral stereocenter.^[ref]

Why care about this distinction? Two enantiomers can fit differently into an already chiral molecule, just as two opposite hands fit differently into one glove. Thus a protein's spatial arrangement can distinguish a mirror pair even when an achiral measurement cannot. Polarimetry provides a different kind of test: it measures a sample's net optical rotation, which depends on the populations of its enantiomers.

There are two, two and four stereoisomers, respectively; all eight individual stereoisomers are chiral. The drawings below give the mirror pairs. Solid and hashed wedges distinguish opposite faces; ordinary changes between conformers are not counted again.

Unlike the usual rapidly inverting trialkylamine, a pyramidal phosphine can retain a phosphorus configuration on an ordinary observational timescale; its two phosphorus configurations must therefore be included.