In chemistry, a nonclassical ion usually refers to carbonium ions, a family of organic cations. They are characterized by delocalized three-center, two-electron bonds. The more stable members are often bi- or polycyclic.
Historically, nonclassical ions were invoked to explain unusually fast solvolyses of steroidal, norbornyl, and cyclopropyl halides. Explanations for these rates was once controversial.
The 2-norbornyl cation is one of the best characterized carbonium ions:
In fact, it has emerged as the prototype for non-classical ions. As indicated first by low-temperature NMR spectroscopy and confirmed by X-ray crystallography, it has a symmetric structure with an RCH<sub>2</sub><sup>+</sup> group bonded to an alkene group, stabilized by a bicyclic structure.
Solvolyses of cyclopropylcarbinyl, cyclobutyl, and homoallyl esters are also characterized by very large rates, and have been shown to occur via a common nonclassical ion structure in the form of a bicyclobutonium ion.