Carbocations:

The history of carbocations dates back to 1891 when

G. Merling reported that he added bromine to
tropylidene (cycloheptatriene) and then heated the product
to obtain a crystalline, water-soluble material, C7H7Br. He did not suggest a structure for it;
however, Doering and Knox convincingly showed that it was tropylium cycloheptatrienylium)
bromide (Figure 2.2). This ion is predicted to be aromatic by the Huckel’s rule.
In 1902 Norris and Kehrman independently discovered that colorless triphenylmethanol gave
deep yellow solutions in concentrated sulfuric acid.

In 1962 Olah directly observed the tert-butyl carbocation, by NMR, as a stable species on
dissolving tert-butyl fluoride in magic acid.
Reactions:
Carbanions
Carbanions are trivalent species with sp3 hybridization. The lone pair of electrons occupies
one of the sp3 orbitals, and the geometry is thus tetrahedral.
Radicals
Radicals are
detected by EPR
The distinguishing characteristic of a free radical is the presence of an unpaired electron.
Species with an unpaired electron are said to be paramagnetic. A technique that has been of
more value to organic chemists is that of electron paramagnetic resonance (EPR), which is
also known as electron spin resonance (ESR) spectroscopy. This is a very sensitive method of
detecting radicals, even at concentrations of 10−7 M.
Carbenes
In 1912, Hermann Staudinger (awarded the Nobel Prize in Chemistry, 1953) also converted
alkenes into cyclopropanes with diazomethane and :CH2 as an intermediate. The simplest
chemical example of carbene is methylene (:CH2), identified by Herzberg in 1959.

Carbenes are highly reactive, neutral, divalent derivatives of carbon having only six valence
electrons with a formal charge of zero. They have two covalent bonds (involving four
electrons) and two nonbonding electrons localized on the carbon atom, and an empty
orbital, which makes a carbene very reactive. One well studied carbene is dichlorocarbene
(Cl2C:), which can be generated in situ from chloroform and a strong base.
Simmons–Smith Reaction
Nitrenes

Although the triplet state is

the common ground state
for most simple nitrenes,
they exhibit sluggish
reactivity.
Benzyne
Arynes were first postulated by Georg Wittig in 1940 followed by Roberts in 1953.
 Ketene

Source Book: M. S. Singh, Reactive Intermediates in Organic Chemistry, Wiley, 2014.