CARBENES

OBJECTIVES:
STUDENTS SHOULD BE ABLE TO:
1.Understand the basic principles involved in the formation of
carbenes and their properties
2.Recognize and know the key types of elementary reactions
involving carbenes
3.WRITE MECHANISMS for reactions involving the formation
and reactions of carbenes

Carbenes are uncharged, electron deficient molecular species

that contain a divalent carbon atom surrounded by a sextet of
electrons.

Carbenes are a family of organic

molecules composed of a neutral

divalent carbon atom with a sextet of

electrons and two substituents.

States of Carbenes
Singlet state: carbocation-like in nature, trigonal

planar geometry, electrophilic character

Triplet state: diradical-like in nature, linear

geometry

 The structure, stability and reactivity of carbenes is very

dependent on the electron configuration of the carbenic atom.

The major division that is used to classify carbenes is whether

the two non-bonding electrons are paired (singlet) or unpaired

(triplet).

py

p
py

px
px
Triplet
sp-hybridized

Singlet
sp2-hybridized

Although in theory there could be 4 possible electron

configurations (Figure 3), in practice only the first three
configurations are ever observed for ground state species.
The vast majority of stable carbenes are of
the singlet ( 2) type.
The relative stability of the singlet and
triplet states depends on the energy
difference between the p and the orbitals.

The relative stability of the p and the orbitals

is determined by the nature of the substituents
adjacent to the carbenic center.
This means that, at least for carbon, we can
control the multiplicity of the molecule by
choosing appropriate substituents.

A variety of factors must be considered to determine whether a

particular group will tend to favour singlet or triplet. These
include the steric properties of a substituent and the influence the
group has on the electronic structure of the compound. The
electronic consequences of a substituent can be subdivided into
inductive effects and mesomeric (resonance) effects.
Inductive effects can be understood in terms of the electronegativity
of the atom bonded to the carbene atom

Resonance effects are best understood in terms

of the -acidity or basicity of the substituent
adjacent to the carbenic center.
The classes of substituent are thus generally
divided into the categories of:
-donors (X), such as halogens, etc.
or
-acceptors (Z), such as SiR3, BR2, metals etc.

Mesomeric
species.

effects

generally

favour

singlet

Cl

C
H

methylene

Cl

dichlorocarbene

C
R

diaminocarbenes

C
N

cyclic diaminocarbenes

C
B

R
R

diborocarbene

Formation

reactions of carbenes:

a)

_
R2 C N N

b)

R2 C C O

c)

RCHX 2 +base

h
or

h
or

R C R + N2
(singlet)
R C R + CO
(singlet)
_ _ _
X
R CX 2

d)

RCHX 2 + R'Li
(whereX=I&Br)

R'X

e)

RCHX 2 + R'Li
(whereX=F&Cl)

R'H

f)

CH2 I2

ZnCu
ether

H
R C Li
X
X
R C Li
X

R C X
R C H + LiX
(carbenoid)
R C X + LiX
(carbenoid)

I CH2 Zn I (SimmonsSmithreagent)
acarbenoidspeciesthatreactsstereospecifically
withalkenestogivecyclopropanesbutdoesnot
insertintoalkaneCHbonds

 Diazoalkanes

R2C

R2C

R2C

hv or heat

N2

R2C

R2C

Sulfonylhydrazones

R2C

NH
SO2Ar

Base

N
SO2Ar

Halides

Cl
H

C
Cl
Cl

Base

Cl
C
Cl
Cl

alpha-elimination

Cl2C

Cl

GENERATION OF CARBENES:
(1) -ELIMINATION OF HX OR X2 FROM AN ORGANIC HALIDE

X
C
Y

- X, -Y

C:

-ELIMINATION OF N2 FROM DIAZO-COMPOUNDS

R1
R2

+ _
C N N

or h
or[M]

R1
C:
R2

+ N2

-Carbonyl

diazo-compounds

Important

precursors of -carbonyl carbenes:

+ _
xs.CH2=N=N

RCOCl

RCOCl+

(Diazomethane)

+ _
RCOCH=N=N

+ _
CH2=N=N

_
+
CH2NN

_
+
CH2NN

+
RCOCH2NN+Cl

+
RCOCHNN

+ _
RCOCH=N=N+H+

H
_ +
CH2NN

+HCl

CH3Cl+N2

H
R

C + _
C
N
N
O

C +
C
N
N
_
O

Carbonyl
diazocompound
H
R

C +
C
N
N
_
O
Diazonium
enolate

Diazonium
enolate
,[Rh]
N2

H
R

O
Carbonylcarbene

SUMMARY
STUDENTS SHOULD BE ABLE TO ACCOUNT FOR THE FORMATION AND

STABILITY OF CARBENES
STUDENTS SHOULD BE ABLE TO RECOGNISE REACTIONS THAT LEAD TO

THE FORMATION OF CARBENES AND HOW THEY GIVE RISE TO ACTIVE

CARBENES
STUDENTS SHOULD BE ABLE TO WRITE MECHANISMS FOR THE

FORMATION OF CARBENES

STUDENTS ARE REQUIRED AT ALL TIMES TO GIVE CLEAR DRAWINGS,

MECHANISMS, POINT FORM EXPLANATIONS WHERE APPROPRIATE AND

MOST OF ALL SHOW CORRECT ARROW MOVEMENT AND BE PRECISE!!

END OF LECTURE

DR. RUSSEL RAMSEWAK