ADVANCED ORGANIC CHEMISTRY I (MPC 102T) UNIT- I: Basic Aspects of Organic Chemistry

CARBENE
A carbene is a species that has a formally neutral carbon atom bearing with a valence of two and two unshared
valence electrons. A carbene has the following general structural formula.

R1 and R2 could be any ligand

Carbenes can react as both electrophile as well as nucleophile.

A carbene could exist in two spin states: singlet carbene and triplet carbene.
(i) In a singlet carbene, the two nonbonded valence electrons in the electron-deficient carbon are in the same
orbital, i.e., they are a lone pair.

(ii) In a triplet carbene, the two nonbonded valence electrons in the electron-deficient carbon are in different
orbitals. Since a triplet carbene has unpaired electrons, it is, by definition, a radical.

1 Bond angles are 125-140° for triplet methylene and 102° for singlet methylene. Both are sp2 hybridised
with bent Shape.
2 In Triplet carbene, One nonbonding unpaired electron is present in p orbital and other in sp2 orbital
3 Singlet carbene is similar to carbocation.
4 Triplet carbene is the more stable state and Singlet is the excited state species
5 Substituents that can donate electron pairs e.g., halogens, may stabilize the singlet state by delocalizing the
pair into an empty p-orbital. No Corresponding stabilisation possible for triplet carbene due to
unavailability of vacant orbital at carbon.
6 When there is a substituent with lone pairs, the singlet carbene is generally more stable than the triplet
carbene. Dichlorocarbene is more stable in singlet.
7 Hence
Order of stability of singlet carbene: :CH2 > :CF2 > :CCl2 > :CBr2 > :CI2

Order of Stability of Triplet Carbene: :CI2 > :CBr2 > :CCl2 > :CF2

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ADVANCED ORGANIC CHEMISTRY I (MPC 102T) UNIT- I: Basic Aspects of Organic Chemistry

Singlet and Triplet Carbenes-which is more stable and why?

Sl.No. Singlet Carbenes Triplet Carbenes

1

2 All electrons are paired and non-bonding electrons Two nonbonding electrons are unpaired and one is
are present in sp2 orbital. present in p orbital and other in sp2 orbital.
3 Singlet carbene often has electrophilic or It has two unpaired electrons. Triplet carbene often
nucleophilic character. has radical-like character.
4 Energy: Energy of two electrons in sp2 orbital
Energy: Energy of one electron in p orbital and
and pairing energy (required for pairing up these
one in sp2 orbital.
two electrons).
5 Energy: two sp2 orbital electron + pairing energy > one p orbital electron + one sp2 orbital electron
Since stability is inversely proportional to energy, hence triplet carbene is more stable than singlet
carbene.

6 Stability: Triplet carbene > Singlet carbene

Carbene Configuration: Triplet vs. Singlet

- Due to electron repulsion, there is an energy cost in pairing both electrons in the σ-orbital. If a small energy
difference between the σ and p-orbitals exists, the electrons will remain unpaired (triplet). If a large gap exists
between the σ and p-orbitals the electrons will pair in the σ- orbital (singlet).
Carbenes: Electronic Structure

Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 22
E-mail: logonchemistry@gmail.com; phytochemistry@rediffmail.com
ADVANCED ORGANIC CHEMISTRY I (MPC 102T) UNIT- I: Basic Aspects of Organic Chemistry

Formation of Carbenes:
Carbenes are neutral species containing a carbon atom with only six valence electrons. Carbenes are usually
formed from precursors by the loss of small, stable molecules.

Type of carbene Method of formation

Decomposition of diazocarbonyl compounds

-elimination of chloroform with base

Thermal decomposition via hydrazone compound

1. Carbenes formation from diazocarbonyl compounds

Diazocarbonyl compounds are much more stable than diazomethane. This is because the electron-withdrawing
carbonyl group stabilizes the diazo dipole, so diazocarbonyls are a useful source of carbenes carrying a
carbonyl substituent.

2. Carbenes formation via alpha elimination

elimination (eliminations in which both the proton and the leaving group are located on the same atom)
occurs when a strong base removes an acidic proton adjacent to an electron withdrawing group to give a
carbanion. Loss of a leaving group from the carbanion creates a carbene.
One of the best known elimination reactions occurs when chloroform is treated with base, forming a
dichlorocarbene.

3. Carbenes formation thermal decomposition via hydrazone compound

Carbenes can be made from diazoalkanes if the diazoalkane is just an intermediate in the reaction and not the
starting material. Good starting materials for these reactions are tosylhydrazones.

Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 23
E-mail: logonchemistry@gmail.com; phytochemistry@rediffmail.com
ADVANCED ORGANIC CHEMISTRY I (MPC 102T) UNIT- I: Basic Aspects of Organic Chemistry

Reactions Of Carbenes:
Carbenes are highly electron-deficient since the carbene carbon has only 6 electrons in the valence shell.
Hence carbenes are highly electrophilic species.
This is reflected in the three major classes of carbene reactions.
(i) Carbene insertions
(ii) Carbene additions
(iii) Carbene rearrangements

(i) CARBENE INSERTIONS

Insertion into single bonds:

Addition to multiple bonds - formation of 3-membered rings:

R1 A R1 A
C: + C
B B
R2 R2
(ii) CARBENE ADDITIONS
The reactions of carbenes are of great synthetic use in the preparation of compounds that have three-
membered rings.

(Methylene adds to the double bond of alkenes to form cyclopropanes)

- Methylene (:CH2), the simplest carbene, can be prepared by the decomposition of diazomethane (CH2N2).

- The structure of diazomethane is a resonance hybrid of three structures

(iii) CARBENE REARRANGEMENTS

Mechanism: 1,2 migration of hydride or a carbanion:

Migratory aptitude: R = H >> aryl > alkyl

Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 24
E-mail: logonchemistry@gmail.com; phytochemistry@rediffmail.com