Question

What is a triplet carbene what is a singlet carbene and how to calculate spin multiplicity of a carbene?

Answer 1

a carbene is a moleculecontaining a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is R-(C:)-R' or R=C:.

The term "carbene" may also refer to the specific compound H2C:, also called methylene, the parent hydride from which all other carbene compounds are formally derived.[1][2] Carbenes are classified as either singlets or triplets, depending upon their electronic structure. Most carbenes are very short lived, although persistent carbenes are known. One well-studied carbene is dichlorocarbene Cl2C:, which can be generated in situ from chloroformand a strong base.

Singlet and triplet carbenes

The two classes of carbenes are singletand triplet carbenes. Singlet carbenes are spin-paired. In the language of valence bond theory, the molecule adopts an sp2hybrid structure. Triplet carbenes have two unpaired electrons. 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 paramagneticand 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 silicoexperiments suggest that triplet carbenes can be thermodynamically stabilized with electropositive heteroatoms such as in silyl and silyloxy carbenes, especially trifluorosilyl carbenes.

Answer 2

Triplet carbene have two unpaired electrons.
Triplet carbenes are paramagnetic and may be observed by electron spin resonance spectroscopy if they persist long enough.
Singlet carbenes are spin paired.In the language of valence bond theory ,the molecules adopts an sp2 hybrid structure.
In spectroscope and quantum chemistry ,the multiplicity of an energy level is defined as
2s+1 ,where s is the total spin angular momentum[1][2].State with multiplicity 1,2,3,4,5 are respectively called singlets ,doublets ,triplets ,quartets ,quintets [2].