carbonium ion

/kahr boh"nee euhm/

an organic ion containing a positively charged carbon atom (opposed to carbanion).

[CARBON + -IUM]

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▪ chemical ion

Introduction

      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 (chemical intermediate).

      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.

Classification.

      Two distinct classes of carbonium ions have come to be recognized. The first are the “classical” carbonium ions, which contain a trivalent carbon atom centre. The carbon atom is in an sp² state of hybridization—that is, three electrons of the carbon atom occupy orbitals formed by the combination (hybridization) of three ordinary orbitals, one denoted s and two, p. All three orbitals lie in one plane; thus, the cationic centre of the molecule formed by bonding the carbon atom with three other atoms or groups tends to be planar. The parent for these ions is the methyl cation, with the formula CH⁺₃ . Schematically, the structure is as shown below (the solid lines representing bonds between atoms):

      The second class of carbonium ions includes the pentacoordinated, or “nonclassical,” carbonium ions, which have three single bonds, each joining the carbon atom to one other atom, and a two-electron bond that connects three atoms, rather than the usual two, with a single electron pair. The parent structure for these ions is that of the methonium ion, CH⁺₅ , in which the dotted lines represent a three-centre bond:

      It is frequently possible to distinguish between these two types of carbonium ions experimentally, as, for example, by the use of certain instrumental methods. These methods include nuclear magnetic-resonance spectroscopy, which gives information about atomic nuclei; infrared and Raman spectroscopy, which are based on light absorption; and, more recently, X-ray-induced electron-emission spectroscopy, which gives information about bond energies.

Preparation and stability.

      Several methods are known for the generation of carbonium ions. They may all, however, be classified in one of the following categories: (1) heterolytic (unsymmetrical) cleavage of the two-electron bond between a carbon atom and an attached group; (2) electron removal from a neutral organic compound; (3) addition of a proton, or other cation, to an unsaturated system; and (4) protonation, or alkylation (addition of an alkyl, or hydrocarbon, group), of a carbon–carbon or carbon–hydrogen single bond. Since carbonium ions are positively charged species, they are most readily formed in relatively polar solvents (solvents consisting of molecules with unsymmetrical distribution of electrons), which help disperse their charges or the charges on the accompanying negative ions throughout the medium. Commonly used solvents include methanol, aqueous acetone, acetic acid, and trifluoroacetic acid.

      The fate of a carbonium ion produced by one of these methods is determined essentially by two factors: (1) the nature of the medium in which the ion is generated and (2) the inherent stability of the ion itself. Carbonium ions react rapidly with the solvent or with any available substance attracted to positively charged entities. Therefore carbonium ions have only a fleeting existence, and indirect methods must be used for their study. The common methods are kinetics (measurements of rates of reaction), chemical analysis of the product formed by reaction of the carbonium ion (particularly, determination of spatial arrangements of atoms in a molecule), and isotopic labelling (that is, the use of radioactive isotopes to identify particular atoms).

      Solvents have been found that do not react with many carbocations. These solvents are hydrogen fluoride–antimony pentafluoride and fluorosulfuric acid–antimony pentafluoride with sulfur dioxide or sulfuryl chloride fluoride also present. In these solvents, the lifetime of many carbonium ions is sufficient to allow direct observation.

      Tertiary carbonium ions are generally more stable than secondary carbonium ions, which, in turn, are more stable than primary ones. In tertiary carbonium ions, the sp² carbon is bonded to three alkyl groups; in secondary carbonium ions, the sp² carbon atom is bonded to two alkyl groups and one hydrogen atom; in primary carbonium ions, the sp² carbon is bonded to either one alkyl group and two hydrogen atoms or, in the case of the methyl cation, three hydrogen atoms. Examples of each are shown below.

      This order of relative stability is explained on the basis of the ability of an alkyl group to disperse the charge on the sp² carbon atom.

      Benzyl cations are more stable than most primary cations because in the benzyl ions the positive charge can become distributed among the carbon atoms of the aromatic ring so the cation can exist in many forms, all of which contribute to the overall structure. Such forms of the benzyl cation are shown below:

      In these structures the benzene ring is indicated by a hexagon, each corner of which is considered to be a carbon atom (the attached hydrogens not being shown). The form with a circle in the hexagon represents structures with alternating single and double bonds in the ring; the other forms are those in which charges appear at various locations in the ring.

Reactions.

      Since carbonium ions are electron-deficient entities, they react with any electron-donor molecules, which are also referred to as nucleophiles (nucleophile). There are three types of nucleophiles: n-bases, pi bases, and sigma bases, in which n, pi, and sigma refer to the bonding state of the donor-electron pair in the nucleophile—that is, nonbonded, pi-bonded, and sigma-bonded, respectively. (Sigma bonds are ordinary covalent bonds between atoms, and pi bonds are the special bonds that occur in unsaturated and aromatic systems.) The nucleophile may be either external or internal (that is, constituting a portion of the cation itself). In the latter case, rearrangement may occur. Examples of the various possible reaction types are shown below:

      1. Reaction with external n-base: acid-catalyzed hydration (addition of water) of isobutylene. In this reaction, there is an unshared (nonbonded) electron pair on the oxygen atom of the water molecule:

      2. Reaction with external base: alkylation of benzene using isopropyl chloride (Friedel–Crafts reaction). Benzene acts as the donor molecule, with the donated electrons coming from the pi-bonded system of the benzene ring:

      In the above equation, the partial circle with the plus charge in the hexagon stands for those forms of the cation in which the positive charge is distributed around the ring (as in the benzyl cation, pictured above).

      3. Reaction with external sigma base: hydride transfer reaction in which the donor electron pair comes from the carbon–hydrogen sigma bond in isobutane:

      4. Reaction with internal n-base: cyclization reaction, with nonbonded electron pair on an oxygen atom serving as donor:

      5. Reaction with internal pi base: acid-catalyzed cyclization to form β-ionone, with the donor electrons coming from the pi electrons of the unsaturated system:

      6. Reaction with internal sigma base: acid-catalyzed rearrangement of neopentyl alcohol, the electron pair coming from an internal carbon–carbon sigma bond:

      Each of these reaction types is widely employed in synthetic organic reactions, and the many acid-catalyzed hydrocarbon transformation reactions are fundamental in petroleum chemistry and in vital bio-organic processes. An important process in the manufacture of high-octane gasoline, for example, consists of the acid-catalyzed isomerization of straight-chain hydrocarbons to branched-chain hydrocarbons. One example of the significance of carbonium ions in bio-organic processes may be found in the biological synthesis of the important material cholesterol from a precursor, squalene, by way of another compound, lanosterol. In this transformation, acid-catalyzed rearrangements—reaction type 6, described earlier—occur repeatedly.

George A. Olah Paul R. Clifford Ed.

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.

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