Reactive Intermediates

Carbenes

Structure and geometry of carbenes

• The divalent carbon intermediates Carbene chemistry has experienced
tremendous growth and broad interest in the past few decades.
• They do not respect the ‘‘octet rule,’’ carbenes have long been considered as
fleeting intermediates in molecular chemistry.
• These fascinating species are involved in many reactions of high synthetic
interest.
• The search for carbene began 150 years ago, at a time when the tetravalency of
carbon was not established.
• The French chemist attempted to prepare methylene (CH 2) by treatment of
methanol with water-abstracting reagents such as P 2O5 or concentrated H2SO4,
assuming that CH3OH is a 1 : 1 adduct of CH2 and H2O.
• Carbenes were first been postulated by Eduard Buchner in 1903 in
cyclopropanation studies of ethyl diazoacetate with toluene.
• In 1912, Hermann Staudinger (awarded the Nobel Prize in Chemistry, 1953) also
converted alkenes into cyclopropanes with diazomethane and :CH2 as an
intermediate.
• The simplest chemical example of carbene is methylene (:CH2), identified by
Herzberg in 1959.
• The name carbene, apparently conceived by Woodward, Doering, and Winstein
was first introduced at a meeting of the American Chemical Society in 1951. The
term ‘‘carbene’’ refers to the specific compound H2C:, the parent hydride from
which all other carbene derivatives are formally derived.
• Carbenes are highly reactive, neutral, divalent derivatives of carbon having only six
valence electrons with a formal charge of zero.
• They have two covalent bonds (involving four electrons) and two nonbonding
electrons localized on the carbon atom, and an empty orbital, which makes a carbene
very reactive.
• One well studied carbene is dichlorocarbene (Cl 2C:), which can be generated in situ
from chloroform and a strong base.
• Doering, in 1954, demonstrated the synthetic utility of dichlorocarbene. However,
despite the explosive growth of knowledge about carbenes, attempts to isolate them
before 1990 remained unsuccessful.
• Nowadays, the term is universally used for divalent carbon species, which are simply
named as substituted derivatives of carbene.
• The exceptions to this are carbenes in which the divalent carbon is part of a ring or is
doubly bonded. These are named using the -ylidene suffix (IUPAC system), for example,
cyclohexylidene and vinylidene (Table 5.2).
• Carbenes are classified as either singlets or triplets depending upon their
electronic structures.
• If the two orbitals are equivalent, according to Hund’s rule the electron
should be assigned to different orbitals with parallel spins.
• On the other hand, if the two available orbitals are not degenerate the two
electrons would probably occupy the lower of the two orbitals with
consequent spin pairing.
• Singlet carbenes have a pair of electrons in the highest occupied molecular
orbital (HOMO) σ, the pπ orbital being vacant with a sp2 hybrid structure.
• As a result, singlet carbenes exhibit both nucleophilic and electrophilic
character.
• Triplet carbenes have two unpaired electrons. They may be either sp2
hybrid or linear sp hybrid.
• Figure 5.1 shows some representations for different electronic states that could
be proposed for methylene. Depending on whether the nonbonding electrons are
of the same or opposite spin, they are triplet or singlet species.
• In 1a the two nonbonding electrons are in the same orbital with opposite spin,
which assumes sp2 hybridization at carbon with two unshared electrons in a sp2
orbital. The p orbital is unoccupied.
• In 1b and 1c they are in separate orbitals, so these two electrons may or may not
have paired spins. Structures 1a and 1b are called singlet states (spin multiplicity
=1), since the nonbonded electrons have their spins paired.
• In 1c one of the two unpaired electrons is in an sp2 and the other in a
p orbital, the spins of the nonbonded electrons are not paired, and so
this is a triplet state (multiplicity=3).
• Hence, triplet carbenes with their unpaired electrons exhibit
properties of diradicals, and under suitable conditions can be
detected by ESR (electron paramagnetic resonance) spectroscopy.
• In linear carbenes, the carbene carbon is sp hybridized (1d). The
bonds in the corresponding triplet carbene structure are formed from
sp orbitals, with the unpaired electrons being in two orthogonal p
orbitals (1d).
• Triplet carbenes are generally stable in the gaseous state, while singlet
carbenes occur more often in aqueous media.
• Bulky substituents clearly kinetically stabilize all types of carbenes.
Moreover, if electronic effects are negligible, the steric effects may also
dictate the ground-state spin multiplicity.
• Singlet carbenes can be kinetically stabilized by introduction of bulky
substituents in the α-position of the carbene center.
• Thermodynamic stabilization of the singlet state can be achieved,
indeed, by interaction of the carbon orbitals, σ and pπ, with appropriate
substituents.
• σ-Electron-withdrawing and π-electron-withdrawing substituents
stabilize the σ orbital by inductive and mesomeric effects, respectively,
while π-electron donating groups (X= OR, SR, NR2, Br, etc.) raise the
energy of the vacant pπ orbital (Figure 5.4).
• Combination of these effects leads to an increase in the σ–pπ gap, thus
favoring a singlet ground state multiplicity.
• The more electron-withdrawing a substituent is the more strongly
electrophilic is the carbene. Thus, difluorocarbene is a more electrophilic
intermediate than dichlorocarbene.
• However, if very strong electron-donor substituents such as amino
groups, methoxy groups, and alkylsulfanyl groups are present then the
carbene may be nucleophilic in its reactions.
• Various singlet carbenes have been characterized as nucleophilic,
ambiphilic (both electron-rich and electron-poor reagent), and
electrophilic species (Scheme 5.1). None of these species, however, have
been detected in solution by spectroscopic methods.
• For example, dimethoxycarbene is lacking of electrophilicity toward
alkenes because of electron donation by the methoxy groups.
• A methoxy group also can be expected to stabilize a carbene, by
interaction of the p orbital of the central carbon atom with a lone pair
of electrons on the oxygen atom (Scheme 5.2).