Carbenes

Group#1 (Jazib,Shams,Shehroz,Danyal
Mursaleen,Mubeen,Junaid)
 Introduction To Reactive Intermediates
(Carbon Species)
• In chemistry, a reactive intermediate or an intermediate is a short-lived, high-energy,
highly reactive molecule. When generated in a chemical reaction, it will quickly convert into
a more stable molecule. Mostly they can not be isolated or stored but in certain conditions
they can be isolated. e.g. (at low temp: and or by matrix isolation).

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• There are some carbon based reactive intermediates shown below

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Carbenes
• As we know that the carbon atom are most stable when they
are of neutral charge. If carbon atom deviates from this
configuration by one way or another, we get an unstable and
there for highly reactive species.

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• Carbenes like carbocation , have six only electrons in their
outer most shell, but in the form of two covalent bonds and
two additional electrons because four of these electron belong
to the carbon atom itself, the carbon is of neutral charge,
though it does not possess full octet. Carbenes tend to react
with neutral partners to form two new bonds, in order to
achieve a full octet and stabilize. Much like carbon radical.

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 Types of Carbene
Singlet Triplet
• Carbon is in ground state • Carbon is in excited state
• Two non boding electrons occupy • Two non bonding electrons occupy
same orbital having apposite spins different orbitals with same spin
• It is paramagnetic

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• It is diamagnetic
• Follows hunds rule
• Violates hunds rule • Changes stereochemistry of end
• Changes stereochemistry of end product when reacting with alkenes
product reacting with alkenes • Its reaction with alkenes are not
• stereospecific means carbons retain stereospecific means carbons of
there stereochemistry reactants change there
stereochemistry Called triplet
• Eg hot methylene
because spin state is 3
• Called singlet because spin sate is • Eg cold methylene
Difference in one
stability is Note: most reactions that produces carbenes do produce singlet carbenes, it is a bit
around 1-8 tricky to generate triplet carbenes. But it is possible that the singlet carbenes form can
Kcal/mol. be converted in the triplet form(interaction with light of a particular wavelength. 4
 Method Of Preparation
(photolysis of di-azomethan)
• Carbenes are molecules with high energy content, they
must be made from high-energy precursors, or extra

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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.
• Most common method

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 Preparation Of Halogenated Carbene
• Halogenated carbenes are formed from halomethanes.
• If chloroform is deprotonated with the strong base, such as hydroxide , it produces the
trichloromathanide anion. To neutralize the formal charge , one of the chlorines can leave in
the form of chloride ion, taking both of the electrons in the carbon chlorine bond with it.

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This leave a halogenated carbenes which again, will be in the singlet form.

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 Reactions of the carbenes
(cyclopropanation)
• The reaction of the methylene carbene
with cic-2-butene. The carbenes is
prepared the carbenes is prepared in
situ, in this case from diazomethane just

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as we have learned, simply in the
presence of the light this will be the slow
step of the reaction since carbenes are
highly reactive ones formed. The
carbenes will insert itself into the pi-
bond to generate th three membered
ring, and doing so the stereochemistry
of alkenes is retained. We can observe
the some reaction with trans-2-butene
and see that the stereochemistry is 7
retained
 Singlet Vs Triplet Carbenes
• Singlet carbene
• We should note that singlet and triplet carbenes react in different ways. Because singlet
carbenes have a lone pair and empty p orbital, they can act as traditional nucleophiles or
electrophiles, though more typically the latter and cyclopropanations with a singlet carbene

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is a concerted reaction. But triplet carbenes do have a lone pair, they are diradicals, meaning
they have two unpaired electrons. As such, they participate in step wise radical additions, in
the stark contrast with the concerted reactions of singlet carbenes. First, one bond

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C-H insertion Of Carbenes
• Carbenes have ability to insert them self's into existing sigma bonds. Which are mostly C-H
bond. This type of chemistry promotes intramolecular cyclization reactions such as given
below. With the liberation of N2 carbenes coordinates to other carbon, hydride shifts over
the first carbon to obtain product,

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Triplet carbenes
• But triplet carbenes do not have a lone pair, they are diradicals, they participate in step wise
radical additions. First, one bond forms between two electrons of opposite spin, but then the
another two electrons have same spin, and therefore cannot pair directly. The system must
wait until one of them flips to the opposite spin, either via radiation emission. This is
typically rather slow, and only once this has occurred may the second bond forms. By

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contrast, triplet carbenes can give mixtures of isomeric products. Any c-c bond in molecule
may have rotated million of times. This distinction alow us to determine the carbenes in the
reaction.

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Isolation
• But how do we know carbenes exist if they cannot be isolated but there are some carbenes
that are stable
• Carbens can be stabilized by back bonding or partial pi bonding
• Group of structures which contain carbene but are stable compounds are N-heterocyclic

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carbenes in this case carbene is stabilized by two adjacent nitrogen atoms
• This compound was first isolated in 1991
• Its formation was confirmed by (NMR) spectroscopy
• 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.
• e.g methylene, the most reactive carbene of all, has been generated in a crystalline matrix of
the inert gas xenon in which it persisted long enough to be studied. Many other carbenes
have been produced by similar matrix isolation techniques.
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Application Of Carbenes
• Formation of cyclopropanes
• Many natural products and biologically active compounds contain cyclopropane rings an
important insecticide pyrethrin contains cyclopropane
• But the problem is cyclopropane is highly unstable due to ring strain that’s why its difficult

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to synthesize but with carbene formation cyclopropane it has become easy
• Ether Can be formed carbene when its trapped in alcohol
• Can also be used for cyclisation which result in hetrocylcic compounds.
• Carbenes can also act as ligands in organometallic complexes forming carbenoids and form
pigments

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Thank
You