Carbene - Structure and Bonding

Structure and Bonding

The two classes of carbenes are singlet and triplet carbenes. Singlet carbenes are spin-paired. In the language of valence bond theory, the molecule adopts an sp2 hybrid structure. Triplet carbenes have two unpaired electrons. They may be either linear or bent, i.e. sp or sp2 hybridized, respectively. Most carbenes have a nonlinear triplet ground state, except for those with nitrogen, oxygen, or sulfur atoms, and halides directly bonded to the divalent carbon.

Carbenes are called singlet or triplet depending on the electronic spins they possess. Triplet carbenes are paramagnetic and may be observed by electron spin resonance spectroscopy 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 (see also Hund's rule of Maximum Multiplicity), 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.