CARBONIUM ION

any member of a class of organic molecules with positive charges localized at a carbon atom. Certain carbonium ions can be prepared in such a way that they are stable enough for study; more frequently they are only short-lived forms (intermediates) occurring during chemical reactions. Carbonium ions are, in fact, one of the most common classes of intermediates in organic reactions, and knowledge of the structures and properties of these substances is fundamental to understanding reactions in which they occur. Many of these reactions are of synthetic, biochemical, or industrial importance. The first carbonium ions were observed in 1901; it was not until 21 years later, however, that German chemist Hans Meerwein concluded that a neutral product (isobornyl chloride) was formed from a neutral reactant (camphene hydrochloride) by rearrangement involving a carbonium ion intermediate. This was the first conceptualization of a carbonium ion as an intermediate in an organic rearrangement reaction. The idea was generalized by the American chemist Frank Clifford Whitmore from 1932 onward and placed on a firm experimental basis by the English chemists Sir Christopher Ingold and E.D. Hughes, beginning in the late 1920s. Although a great deal had been surmised about carbonium ions by indirect methods, it was only after 1960 that general methods for the formation of stable, long-lived carbonium ions became available. Additional reading D. Bethell and V. Gold, Carbonium Ions (1967), is an excellent introduction and has an extensive bibliography. G.A. Olah and P.V.R. Schleyer (eds.), Carbonium Ions, 4 vol. (1968), is a review of particular aspects of carbonium-ion chemistry, with individual chapters written by active researchers in the field.