In chemistry, a carbene is a highly reactive organic compound with the general molecular formula "R1R2C:." This formula indicates that each molecule has a carbon atom (C) attached to two substituents (R1 and R2), and this carbon atom has two additional (valence) electrons in its outermost shell that account for the molecule's high reactivity. Most carbenes are very short lived, but some persistent carbenes are also known. They can be stabilized in the form of organometallic complexes.
Generally, there are two types of carbenes, known as singlet and triplet carbenes. They differ in structure based on the distribution of electrons in orbitals of the reactive carbon atom.
Most carbenes have a nonlinear triplet ground state, except for those with nitrogen, oxygen, or sulfur atoms, and dihalocarbenes.
Carbenes are called singlet or triplet depending on the electronic spins they possess. Triplet carbenes are paramagnetic and may be observed by electron paramagnetic resonance spectroscopy (EPR) if they persist long enough. The total spin of singlet carbenes is zero while that of triplet carbenes is one (in units of ). Bond angles are 125-140° for triplet methylene and 102° for singlet methylene (as determined by EPR). Triplet carbenes are generally stable in the gaseous state, while singlet carbenes occur more often in aqueous media.
For simple hydrocarbons, triplet carbenes usually have energies 8 kcal/mol (33 kJ/mol) lower than singlet carbenes. Thus, in general, triplet is the more stable state (the ground state) and singlet is the excited state species. Substituents that can donate electron pairs may stabilize the singlet state by delocalizing the pair into an empty p-orbital. If the energy of the singlet state is sufficiently reduced, it will actually become the ground state.
No viable strategies exist for triplet stabilization. The carbene called 9-fluorenylidene has been shown to be a rapidly equilibrating mixture of singlet and triplet states with an approximately 1.1 kcal/mol (4.6 kJ/mol) energy difference. It is, however, debatable whether diaryl carbenes such as the fluorene carbene are true carbenes because the electrons can delocalize to such an extent that they become in fact biradicals. In silico experiments suggest that triplet carbenes can be stabilized with electropositive groups such as trifluorosilyl groups.
Singlet and triplet carbenes do not demonstrate the same reactivity. Singlet carbenes generally participate in cheletropic reactions as either electrophiles or nucleophiles. Singlet carbene with its unfilled p-orbital should be electrophilic. Triplet carbenes should be considered to be diradicals, and participate in stepwise radical additions. Triplet carbenes have to go through an intermediate with two unpaired electrons whereas singlet carbene can react in a single concerted step. Addition of singlet carbenes to olefinic double bonds is more stereoselective than that of triplet carbenes. Addition reactions with alkenes can be used to determine whether the singlet or triplet carbene is involved.
Reactions of singlet methylene are stereospecific while those of triplet methylene are not. For instance the reaction of methylene generated from photolysis of diazomethane with cis-2-butene and trans-2-butene is stereospecific which proves that in this reaction methylene is a singlet.
Reactivity of a particular carbene depends on the substituent groups, preparation method, reaction conditions such as presence or absence of metals. Some of the reactions carbenes can do are insertions into C-H bonds, skeletal rearrangements, and additions to double bonds. Carbenes can be classified as nucleophilic, electrophilic, or ambiphilic. Reactivity is especially strongly influenced by substituents. For example, if a substituent is able to donate a pair of electrons, most likely carbene will not be electrophilic. Alkyl carbenes insert much more selectively than methylene, which does not differentiate between primary, secondary, and tertiary C-H bonds.
Carbenes add to double bonds to form cyclopropanes. A concerted mechanism is available for singlet carbenes. Triplet carbenes do not retain stereochemistry in the product molecule. Addition reactions are commonly very fast and exothermic. The slow step in most instances is generation of carbene. A well-known reagent employed for alkene-to-cyclopropane reactions is Simmons-Smith reagent. It is a system that includes copper, zinc, and iodine, where the active reagent is believed to be iodomethylzinc iodide.
Carbenes are also involved in insertion reactions, in which the carbene interposes itself into an existing bond. The order of preference is commonly: (1) X-H bonds, where X is not carbon; (2) C-H bond, and (3) C-C bond. Insertions may or may not occur in single step.
Intramolecular insertion reactions present new synthetic solutions. Generally, rigid structures favor such insertions to happen. When an intramolecular insertion is possible, no intermolecular insertions are seen. In flexible structures, five-membered ring formation is preferred to six-membered ring formation. Both inter- and intramolecular insertions are amendable to asymmetric induction by choosing chiral ligands on metal centers.
Alkylidene carbenes are alluring in that they offer formation of cyclopentene moieties. To generate an alkylidene carbene a ketone can be exposed to trimethylsilyl diazomethane.
Carbenes may be produced by a number of different reactions, some of which are noted below.
Carbenes can be stabilized as organometallic species. These transition metal carbene complexes fall into the following three categories, of which the first two are the most clearly defined:
An additional group of carbenes, known as foiled carbenes, derive their stability from the proximity of a double bond—that is, their ability to form conjugated systems.
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