carbene

/kahr"been/, n.

the radical CH₂ and its derivatives.

[CARB- + -ENE]

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▪ chemistry

Introduction

      any member of a class of highly reactive molecules containing divalent carbon atoms—that is, carbon atoms that utilize only two of the four bonds they are capable of forming with other atoms. Occurring usually as transient intermediates during chemical reactions, they are important chiefly for what they reveal about chemical reactions and molecular structure. In addition, some chemical compounds, particularly those in which the molecules contain carbon atoms arranged in small rings, can best be prepared by the use of carbenes.

      According to the electronic theory of bonding, bonds between atoms are formed by a sharing of electrons. In terms of this theory, then, a carbene is a compound in which only two of the four valence, or bonding, electrons of a carbon atom are actually engaged in bonding with other atoms. By contrast, in multiple bonded compounds, such as hydrogen cyanide, all four of the valence electrons of the atoms are involved in bonds with other atoms. Because there is no excess or deficiency of electrons in the molecules of carbenes, they are electrically neutral (nonionic).

Early investigations.

      Because of the great reactivity of carbenes, they normally have very short lifetimes, and it is not surprising, therefore, that unambiguous and direct experimental evidence of their existence has been obtained only recently. Divalent carbon compounds had been postulated, however, as long ago as 1876, when it was proposed that dichlorocarbene, Cl−C−Cl, was an intermediate in the base-catalyzed hydrolysis (decomposition brought about by water) of chloroform (HCCl₃). Toward the end of the 19th century, an extensive theory had been developed that postulated divalent carbon compounds as intermediates in many reactions. Later work, however, disproved many of these postulates, and, as a result, carbenes were no longer put forward as hypothetical reaction intermediates. Carbene chemistry revived in the 1950s after unambiguous evidence had demonstrated their existence and studies by several methods had yielded detailed information about their structures.

electronic configuration and molecular structure.

      The theory of chemical bonding predicts two fundamentally different electron configurations for carbenes, either one of which may correspond to the ground state of the molecules (state of lower energy content) depending only on the nature of the atoms and groups attached to the divalent carbon atom. This duality arises from the fact that the two bonds of the carbene utilize only two of the four valence orbitals (orbital) on carbon—orbitals being the regions occupied by the various electrons in an atom. The two valence orbitals of the carbon atom not used in bonding are available to accept the two nonbonding electrons. In general, each orbital can accommodate two electrons if their spins are paired—that is, if the angular momenta are of opposite sign. There are thus two possible distributions of the nonbonding electrons: they may be in the same orbital and have paired (opposite) spins, or they may be divided between the two available orbitals and have parallel spins. Substances with electrons having parallel (or unpaired) spins show a magnetic effect (moment). In a magnetic field this moment may be parallel, perpendicular, or antiparallel (parallel but proceeding in the reverse direction) to the direction of the field; these three possible alignments correspond to three forms of slightly different energy, and, as a result, substances with unpaired electrons can exist in all three forms and are said to be in a triplet state. By contrast, substances with all electrons paired show no net magnetic moment and are referred to as singlet states. In principle, carbenes can exist in either the singlet or triplet state (depending upon whether the electrons are in the same or different orbitals, respectively).

      In most organic compounds (compounds of carbon), the singlet state is more stable than the triplet state, and the normal or ground state of the molecule is of this form. In these compounds triplets occur only as excited or high-energy states. In carbenes, on the other hand, because of the two nonbonding electrons and the two vacant orbitals, it is expected on theoretical grounds that the triplet state should be of comparable stability to the singlet state and may, in fact, be the ground state.

 Theoretical considerations also suggest that the carbene carbon atom and the two atoms joined to it are arranged in a “V” rather than in a linear fashion—that is, the bonds from the carbon atom to the two substituent atoms are situated at an angle that is less than 180°—in both the triplet and the singlet states. The bond angle for the singlet state, however, is predicted to be larger than that for the triplet state. These predictions are fully supported by experiments. The simplest carbene, methylene, has been shown by a technique called electron magnetic resonance spectroscopy to have a triplet ground state, in which the angle between the carbon–hydrogen bonds equals 136°. The singlet state of methylene, which can be obtained in special circumstances, has been studied by another technique, optical spectroscopy, and its bond angle has been determined to be 104°. The structures and the configurations of the nonbonding electrons of the triplet and singlet states of methylene are shown as A and B in the accompanying drawing—>; the loops represent the orbitals not used in bonding, and the pairing and nonpairing of electron spins are indicated by antiparallel and parallel arrows, respectively. This schematic orbital representation shows both nonbonding orbitals occupied in A (the triplet state) and an empty orbital in B (singlet).

      The structural features that determine whether a singlet or a triplet state corresponds to the lower energy form of the carbene molecule may be summarized by the rule that, with few exceptions, carbenes having only carbon or hydrogen atoms attached to the divalent (carbene) carbon atom have triplet ground states, whereas those with nitrogen, oxygen, and halogen substituents have singlet ground states. Examples of triplet carbenes are methylene (H−C−H), phenylmethylene (C₆H₅−C−H), diphenylmethylene (C₆H₅−C−C₆H₅) and propargylene (HC≡C−C−H). Carbenes with known singlet ground states are methoxymethylene (CH₃O−C−H), chloromethylene (Cl−C−H), and phenylchloromethylene (C₆H₅−C−Cl).

Formation.

      Because carbenes are molecules with high energy content, they must be made from high-energy precursors, or extra energy must be provided from external sources. Chemical transformations induced by light, so-called photochemical reactions, often are used to prepare carbenes, because the energy of the absorbed light is taken into the high-energy structures. Organic compounds containing a diazo group (two nitrogen atoms joined to one another and to a carbon atom by a double bond) are the most frequently used precursors of carbenes. The molecular structure of diazo compounds (diazo compound) is represented by the generalized formula

      in which R and R′ represent two organic groups, which may be the same or different. On either photolysis or pyrolysis (treatment with light or heat, respectively), diazo compounds cleave to yield the corresponding carbene and a free molecule of nitrogen gas. Diazirins, which are ring, or cyclic, compounds, with a structure similar to that of the diazo compounds, undergo the same cleavage reaction and are frequently used as precursors of carbenes. The production of a carbene from a diazo compound occurs as shown below:

      When the photolysis of diazo compounds is carried out at very low temperature in an unreactive solid medium, it is often possible to prevent the resulting carbene from undergoing further reaction. Measurable amounts of the carbene may persist, therefore, in the solid medium, or matrix, for a long time. For example, methylene, the most reactive carbene of all, has been generated in a crystalline matrix of the inert gas xenon (cooled to the boiling point of helium) in which it persisted long enough to be studied. Many other carbenes have been produced by similar matrix isolation techniques.

      The photolytic decomposition of certain ketenes (ketene), substances the molecules of which contain two carbon atoms and an oxygen atom joined by double bonds,

      gives carbon monoxide and carbenes, as shown in the following equation:

      Under certain circumstances, cyclopropanes (cyclopropane), the molecules of which contain three-membered carbon rings, can serve as carbene precursors in photochemical reactions. For example, 1,1,2,2,-tetraphenylcyclopropane is converted to diphenylcarbene by the reaction

      The formation of carbenes by way of electrically charged, or ionic, intermediates is exemplified by the reaction of chloroform with a strong base, potassium tert-butoxide. In the first step of this reaction, a proton or hydrogen ion (H⁺) is removed from the chloroform molecule in a normal acid–base reaction. The resulting potassium trichloromethide then loses potassium chloride to give dichlorocarbene. Other haloforms, compounds conforming to the formula HCX₃, in which X equals an atom of chlorine, bromine, or iodine, react in an equivalent way to form the corresponding dihalocarbenes.

Reactions.

      Methylene is one of the most reactive molecules known and there are few organic compounds able to resist attack by this substance. The reactivity of carbenes is somewhat reduced when stabilization results from the phenomenon known as resonance (resonance, theory of), which is said to occur when alternate electronic structures (called resonance forms) can be written for a single molecular type. The actual state of the molecule is then thought to include characteristics of all the forms and to be more stable than any of them individually. Difluorocarbene and methoxycarbene, for example, are much less reactive than methylene, presumably because the resonance forms shown in the formulas below contribute to internal stabilization.

      In these representations, the various resonance forms of a single hybrid structure are connected by double-headed arrows, and the plus and minus signs indicate positive and negative charges produced by shifts of electrons.

      The various chemical reactions that carbenes undergo can be classified as either intramolecular or intermolecular reactions. Intramolecular reactions, or rearrangements, involve only the carbene itself and include no other outside substances; if structurally possible, they lead to stable molecules in which the carbon atom is in its normal, or tetravalent, state. An example of an intramolecular reaction is the rearrangement of methylcarbene to ethylene, in which a hydrogen atom undergoes a shift from one carbon atom to the next:

      Such an intramolecular rearrangement, of course, is not possible for carbenes composed of only three atoms, such as methylene itself or the halomethylenes.

      Intermolecular reactions are those involving two or more separate molecules. Three important classes of intermolecular reaction of carbenes are known: dimerization, addition, and insertion reactions. Dimerization of carbenes—combination of two molecules of the carbene—gives olefins (olefin), the molecular formulas of which are exactly twice that of the carbene. An example is the formation of tetramethoxyethylene from dimethoxycarbene.

      The addition of carbenes to olefins and acetylenes is a very useful reaction because it constitutes a simple way to synthesize cyclopropanes and cyclopropenes having a great variety of structures. Intramolecular versions of this type of addition reaction are also possible, as shown by the cyclization of allylcarbene generated from the corresponding diazo compound. The resulting bicyclobutane—an unusual compound, which contains a ring system with considerable strain resulting from abnormal angles between bonds—demonstrates the value of carbene reactions for the synthesis compounds difficult to obtain by other methods.

Analytical and physical study.

      Because carbenes occur chiefly as intermediates in the course of chemical reactions, much of their study is conducted by kinetic methods, as the general field of investigation of rates of reaction and the factors that influence them is known. Much of the available information about the structures of carbenes has been obtained by optical spectroscopic methods—that is, by the study of light absorption patterns—which have revealed, for example, the bond lengths and angles in the various carbenes. Electron-spin resonance spectroscopy, the physical method that gives information about the angular momenta of electrons, has been especially useful in differentiating triplet from singlet states.

Gerhard L. Closs

Additional Reading

W. Kirmse, Carbene Chemistry (1964); G.L. Closs, Topics in Stereochemistry, vol. 3 (1968).

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