carbanion

carbanion, any member of a class of organic compounds in which a negative electrical charge is located predominantly on a carbon atom. Carbanions are formally derived from neutral organic molecules by removal of positively charged atoms or groups of atoms, and they are important chiefly as chemical intermediates—that is, as substances used in the preparation of other substances. Important industrial products, including useful plastics, are made using carbanions.

The simplest carbanion, the methide ion (CH^-₃ ), is derived from the organic compound methane (CH₄) by a loss of a proton (hydrogen ion, H⁺) as shown in the following chemical equation:

in which the symbols C and H represent, respectively, carbon and hydrogen atoms; the subscripts indicate the numbers of atoms of each kind included in the molecules; the superscript plus and minus signs indicate, respectively, positive and negative charges; and the double arrows indicate that the reaction shown can proceed in either the forward or the reverse direction, a condition known as reversibility.

Molecular structures.

In discussing the structures of carbanions, one must distinguish between localized and delocalized ions. In the former, the negative charge is confined largely to one carbon atom, whereas, in the latter, it is distributed over several atoms.

Localized ions.

The simplest localized carbanion is the methide ion (CH^-₃). It is isoelectronic (it has identical electron configuration) with the neutral molecule ammonia (formula NH₃, N being the chemical symbol for the nitrogen atom). The geometry of the methide ion is best represented by a pyramid with the carbon atom at the apex, a structure similar to that of the ammonia molecule. Both structures are shown below:

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in which the solid lines represent bonds between atoms and the dotted lines merely indicate the bases of the pyramids.

Delocalized ions.

The allyl carbanion (formula, C₃H^-₅), a somewhat more elaborate unit than the methide ion, serves as the prototype for the structures of delocalized carbanions. It is derived from the substance propene by loss of a proton, as shown in the equation below, and its structure is best characterized by the “resonance” relationship expressed by the two formulas enclosed within square brackets:

A substance (like the allyl carbanion), whose structural formula is expressed in terms of separate resonance forms, is considered to have a hybrid structure similar to all the resonance forms but truly expressed by none of them alone.

An additional example of this kind of carbanion is the benzylic anion (shown below), in which the negative charge can be distributed over a much more extended pi-bond system, which includes an aromatic ring (a circle of carbon atoms joined by sigma and pi bonds). A resonance formulation of this anion is given below:

Closely related to the allyl carbanion are the enolate anions, in which one of the carbon atoms is replaced by an oxygen atom. Enolate ions are derivatives of ketones and aldehydes (compounds containing a double bond between carbon and oxygen atoms), from which they can be generated by abstraction of a proton from the carbon atom that is located next to the carbon of the carbonyl group. The resonance forms of an enolate ion are as depicted below:

Because of the greater attraction for electrons (electronegativity) of oxygen as compared to carbon, the resonance structure with negative charge on oxygen contributes more than half to the true representation of the compound. In a typical enolate ion, in other words, the oxygen atom bears more of the negative charge than the carbon atom.

Ion pairs.

In a solution containing carbanions there must exist a corresponding cation (positive ion) for each carbanion. If the two ions of opposite charge are in close contact with each other, a covalent (nonionic) bond may form. This reaction is represented by the equilibrium that follows:

in which M in most cases is a metal atom. Because for a given carbanion the reaction of ionization is favoured by a low electron affinity of the cation, the largest carbanion character of such a compound is exhibited when the atom M is an alkali metal—lithium, sodium, potassium, cesium, or rubidium. Even in cases in which the tendency to form covalent bonds is negligible, however, the properties of free carbanions cannot always be observed. This situation arises from the fact that there is a strong attraction between the cation and the anion, leading to the pairing of these ions of opposite charge. The resulting “tight” ion pairs can be broken up only if the interactions of the individual ions with the solvent are large enough to overcome the attraction between the ions. Therefore, only in solvents that strongly solvate at least one type of the ions can free carbanions be observed. Examples of solvents with strong tendencies to solvate the cations are ethers and dimethyl sulfoxide. In general, the energy needed to separate ion pairs is larger when the charge on the anion is localized than when it is delocalized. In fact, if the carbanion is derived from a simple alkane compound of carbon and hydrogen, as for example the methide ion (above), no common solvent exists that provides enough solvation energy to separate the ion pairs and that is, at the same time, inert to chemical reaction with the anion. Therefore, alkyl alkali-metal compounds do not dissociate to free ions, and their properties are characteristic of the ion pairs only.

Preparation.

Any preparation of organic-alkali-metal compounds is a source of carbanions. The reaction of organic compounds containing atoms of chlorine, bromine, or iodine with alkali metals is one of the most often used methods. This reaction can be expressed:

in which R is an organic group; X is an atom of chlorine, bromine, or iodine; and M is an atom of an alkali metal.

The conversion of one carbanion into another can be accomplished with either hydrocarbons or organic halides, as shown by the equations below:

Reactions.

Perhaps the most common reaction of carbanions is their action as bases—as shown in the first equation in this article. It is useful to redefine this acid–base equilibrium by the equation:

in which Y is a proton acceptor (base).

Consideration of carbanion formation in terms of such an equilibrium makes it possible to assign a numerical value to the basicity (proton-attracting power) of the carbanion. This is done by determining an equilibrium constant for the equilibrium reaction above; the equilibrium constant is the ratio

in which K_a is the acid equilibrium constant, and the terms in square brackets are the concentrations of the enclosed entities. For convenience equilibrium constants are frequently converted to another quantity, the acidity exponent, which is almost invariably referred to by its symbolic representation, pK_a. The pK_a is the negative logarithm of the equilibrium constant, or mathematically, pK_a = -log K_a. For a given base (Y), increasing basicity of a carbanion is reflected in a decreasing equilibrium constant (K_a) and an increasing pK_a.

The pK_a’s of most carbon acids range from approximately 15 to above 40, indicating that carbanions are much stronger bases than water (which has a pK_a of 15.7). The large variation in pK_a among the different carbon acids reflects the varying degree of internal stabilization in the corresponding carbanions. Generally, three different mechanisms of stabilizing carbanions have been recognized. The first is the already mentioned stabilization by resonance. Examples of resonance-stabilized carbanions are the allyl and benzyl carbanions, each of which has a pK_a of about 35. Particularly large resonance stabilization is encountered in the cyclopentadienyl anion (pK_a about 15), which has an aromatic pi electron system not present in the corresponding hydrocarbon, as shown below:

A second factor lending stability to carbanions is the inductive (electron-withdrawing) effect of neighbouring electronegative atoms. An example is provided by the comparison of the pK_a’s of methane (formula, CH₄), pK_a about 40, and chloroform (CHCl₃), pK_a less than 25. The greater stability of the trichloromethide ion,

which results from removal of a proton from chloroform, can be understood in terms of the inductive effect of the chlorine atoms, which reduces the free charge on carbon and distributes it to the chlorine atoms.

The third effect is based on a change in electronegativity of the carbon atom carrying the negative charge. An example of this effect is the sequence of decreasing pK_a’s from ethane through ethylene to acetylene (the respective pK_a’s being 42, 36, and 25). In the corresponding carbanions, shown below, the negative charge resides on carbon atoms that are, respectively, sp³, sp², and sp hybridized.

Since the electronegativity of the carbon increases with increasing s-character of the bonding (that is, in the order sp³, sp², and sp) the carbanion stability follows the same trend.

A type of reaction that makes carbanions valuable synthetic intermediates is their ability to function as nucleophiles (positive-charge seeking groups) in displacement reactions. Methylsodium, for example, reacts with methyl bromide to give ethane, as follows:

This reaction type is extensively used for the alkylation of ketones. In the process, the ketones are first converted into their enolate ions and then alkylated with a suitable alkyl halide, as in the example below:

Another synthetically useful reaction is the addition of carbanions to carbonyl groups; for example, methyllithium adds to acetone to give lithium tert-butoxide, as shown