DR.

GURUMEET C
WADHAWA

Dr. Gurumeet C Wadhawa

Department of Chemistry
Karmaveer Bhaurao Patil ,College
Vashi, Navi Mumbai
CARBENES AND NITRENES

Carbenes are uncharged,

electron deficient molecular
species that contain a divalent
carbon atom surrounded by a
sextet of electrons.
Nitrenes are uncharged,
electron deficient molecular
species that contain a
monovalent nitrogen atom
surrounded by a sextet of
electrons.
 Triplet carbenes are generally stable in the gaseous state, while
singlet carbenes occur more often in aqueous media.
 The C-atom in singlet carbene is sp2 - hybridized in
which the spin –paired electrons occupy an sp2
orbital.
 Shape of carbenes is planar.
 STRUCTURE AND
BONDING

• Singlet carbenes are spin-paired. This molecule adopts an sp2 hybrid

structure.
• Eg- :CH2 :CHPh :CHPh2 :CHR

• 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.
• Eg:- :CCl2 :CHCl :C(OMe)2
• Singlet state: carbocation-like in nature, trigonal planar
geometry,electrophiliccharacter. . Singlet carbenes generally participate in
cheletropic reactions as either electrophiles or nucleophiles .

• Triplet state: diradical-like in nature, linear geomtry and participate in

stepwise radical additions. Triplet carbenes have to go through an
intermediate with two unpaired electrons whereas singlet carbene can
react in a single concerted step.
 DISINTEGRATION OF
THEIR ANALOGS,VIA
DIAZOALKANES AND
PHOTOLYTIC,THERMAL, OR
TRANSITION METAL (RH, CU)-
CATALYZED ROUTES.
CARBENE
EXAMPLES
FORMATION REACTIONS OF CARBENES
_+
h
a) R2 C N N R C R + N2
or (singlet)

h
b) R2 C C O R C R + CO
or (singlet)
 _ _ _
c) R CX2 X R C X
RCHX 2 + base

H
R'X
d) RCHX 2 + R'Li R C Li R C H + LiX
(where X = I & Br) X (carbenoid)
X
R'H
e) RCHX 2 + R'Li R C Li R C X + LiX
(where X = F & Cl) X (carbenoid)

Zn-Cu
f) CH2 I2 I CH2 Zn I (Simmons-Smith reagent)
ether
a carbenoid species that reacts stereospecifically
with alkenes to give cyclopropanes but does not
insert into alkane C-H bonds
TYPICAL CARBENE REACTIONS

a) Insertion into a -bond: C H + CH2 C CH2 H

b) Addition to a -bond: C C + CH2 C C

C
_ + Y
c) Ylide type rxn: R2 C + X Y R2 C X Y R2 C
X
an ylide

d) Intramolecular insertion:
CH3
H3 C H H3C H H3 C
C C + C +
H3 C C CH 3 H3C CH CH2 H3 C C CH3
CH3
H
(5%) (90%) (5%)
1,2-insertion 1,2-insertion 1,3-insertion

e) Cracking: C H + H C C H

+ + +
f) Dimerization: R2 C N N + CR2 R2 C N N CR2 R2 C CR2 + N2
MECHANISTIC ASPECTS OF CARBENE
CHEMISTRY
Observations
A. Gas Phase Experiment at very low pressure:
_ CH3
+
CH2 N N + CH3 CH2 CH2 CH2 CH3 h CH3 (CH2 )4 CH 3 + CH 3 CH CH 2 CH2 CH3
(I) (II)
~49% ~34%
CH3
+ CH 3 CH 2 CH CH 2 CH 3
(III)
~17%
Point of Information: As the pressure of the system is increased (nitrogen or argon added),
the yields of (II) and (III) increase at the expense of (I).
B. Liquid phase experiment :
+ _ H3 C CH3
CH2 N N + C C h cis-1,2-dimethylcyclopropane
H H (only organic product)

Point of Information: When an inert diluent such as perfluoropropane is added to the starting
materials, a mixture of cis- and trans-1,2-dimethylcyclopropanes is obtained.
 MECHANISTIC ASPECTS OF CARBENE
CHEMISTRY
Explanation for Gas Phase Experiment:
At very low pressure, reactive, singlet carbene inserts in the alkane C-H bonds in a completely
random, statistical manner. However, upon addition of nitrogen or argon gas to the reaction,
singlet carbene reverts to less reactive (more selective) triplet carbene via non-productive collisions
with the inert diluent.Triplet carbene shows a preference for attacking tertiary and secondary
hydrogen atoms rather than primary hydrogen atoms. Hence, formation of more tertiary and
secondary abstraction products at the expense of primary abstraction product.
Explanation for Liquid Phase Experiment:
C3 F 8 CH2 CH2
CH2 CH2
H H C3 F8 H H
singlet triplet C C spin C C
+ + H3C CH 3 inversion H3 C CH3
H diradical
H H H
C C C C rotation
H3 C CH3 H3 C CH3
ring
closure CH2

H CH3
cis product C C
+ H3 C H
H H
H3 C CH3 trans product
cis only ring closure
 Electron paramagnetic resonance spectroscopy(EPRS) can be
used to detect the formation of the triplet carbenes.
 Rotational fine structure of the UV and Visible spectra can
detect the formation of the singlet (bent form) or triplet
(linear form) carbenes.
 π- Insertion reaction also can detect and distinguish the
formation of singlet and triplet.
 NITRENE
 In chemistry, a nitrene or imene (R–N) is
the nitrogen analogue of a carbene.
 The nitrogen atom is uncharged and univalent, so
it has only 5 electrons in its valence level—
one covalent bond and four non-bonded electrons.
 It is therefore considered an electrophile due to
the unsatisfied octet.
 A nitrene is a reactive intermediate and is
involved in many chemical reactions. 
 he simplest nitrene, HN, is called imidogen, and
that term is sometimes used as a synonym for the
nitrene class
 Inn the simplest case, the linear N–H molecule (imidogen) has its
nitrogen atom sp hybridized, with two of its four non-bonded
electrons as a lone pair in an sp orbital and the other two occupying
a degenerate pair of p orbitals.
 The electron configuration is consistent with Hund's rule: the low
energy form is a triplet with one electron in each of the p orbitals
and the high energy form is the singlet with an electron pair filling
one p orbital and the other p orbital vacant.
 As with carbenes, a strong correlation exists between the spin
density on the nitrogen atom which can be calculated in silico and
the zero-field splitting parameter D which can be derived
experimentally from electron spin resonance.
  Small nitrenes such as NH or CF3N have D values around
1.8 cm−1 with spin densities close to a maximum value of 2. At the
lower end of the scale are molecules with low D (< 0.4) values and
spin density of 1.2 to 1.4 such as 9-anthrylnitrene and 9-
phenanthrylnitrene.
 INTRAMOLECULAR INSERTION AND
INTER MOLECULAR INSERTION

• Intramolecular insertion reactions present new

synthetic solutions.
• When an intramolecular insertion is possible, no
intermolecular insertions are seen.
Carbenes will also insert into other
bonds

•Carbene insertion into an O-H bond

Initial attack on the lone pair of hetero atom

• The mechanism involves addition of the oxygen lone pair into

an empty p-orbital on the carbene, followed by proton transfer
to generate a neutral molecule
CARBENE INSERTION INTO AN N-H BOND - MERCK
INDUSTRIAL SYNTHESIS OF A Β-LACTAM
ANTIBIOTIC.

A synthesis of the class of compound as carbapenam around a rhodium

catalysed carbene insertion into a N-H bond.
2.CARBENE
ADDITION

• The stereochemistry of carbene addition to alkenes can be used as

a test of whether the carbene is reacting via the singlet or the
triplet spin state:
Addition of singlet and triplet carbenes to alkenes.

• Singlet and triplet carbenes do not demonstrate the

same reactivity
• Triplet carbenes should be considered to be diradicals,
and participate in stepwise radical additions.
• Triplet carbenes have to go through an intermediate
with two unpaired electrons whereas singlet carbene
can react in a single concerted step.
Alkenes react with singlet carbene in a concerted fashion -
alkene
stereochemistry is preserved in the cyclopropane product:
ALKENES REACT WITH TRIPLET (I.E. DIRADICAL) CARBENE IN A
STEPWISE FASHION - THE ALKENE STEREOCHEMISTRY IS LOST IN
THE CYCLOPROPANE PRODUCT:
Carbene additions to arenes: 6 7 ring-expansion to yield cyclohepta-
trienes:
• Step 1:
• The reaction mechanism of a Buchner ring expansion begins with
carbene formation from ethyl-diazoacetate generated initially
through photochemical or thermal reactions with extrusion of
nitrogen.

• The generated carbene adds to one of the double bonds of

benzene to form the cyclopropane ring.
3.CARBENE
REARRANGEMENT
• Wolff rearrangement
• The Wolff rearrangement is a reaction in organic chemistry in
which an α-diazocarbonyl compound is converted into a ketene by
loss of dinitrogen with accompanying 1,2-rearrangement.
• The Wolff rearrangement yields a ketene as an
intermediate product, which can undergo nucleophilic attack
with weakly acidic nucleophiles such as water, alcohols, and
amines, to generate carboxylic acid derivatives
• The Wolff rearrangement can be induced via
thermolysis,photolysis,or transition metal catalysis.
 (1) Carbene Rearrangement
Mechanism: 1,2 migration of hydride or a carbanion:

Migratory aptitude: R = H >> aryl > alkyl

ARNDT-EISTERT
REACTION

• One important application of this reaction is the chain extension of

acyl chlorides to their homologous esters known as the arndt-
eistert reaction.
Arndt-Eistert Reaction - homologisation of carboxylic acid
derivatives:
 NITRENES
 These are neutral reaction intermediates where the
central nitrogen atom is electron-deficient and has a
sextet of electrons.

 Sp2 hybridized and

planar in shape.
GENERATIONS OF NITRENES
 Like carbenes , these are also generated by protolytic ,thermal,
or base –catalysed α-elimination reactioOns. For eg;
O
hv
R N N
+
N
-
R N
+ N2

Acyl azides Acyl nitrene

hv
R N N
+
N
-
R N + N2

Alkyl azides Alkyl nitrene

 O
O Br
-
+ H2 + Br
-

N + HO
H3C N
R H
Acyl nitrene
N-bromo amides

 By reduction of nitro compounds with trialkyl

O
phosphites.
Ph
+ +
+
N (OEt) 3P Ph N (OEt) 2
-
O O

(OEt) 3P
O

Ph N P
+ (OEt) 3
 NITRENE FORMATION REACTIONS
_ +
h
a) R N N N R N + N2
or
R = alkyl,aryl, H 
_ +
R SO2 N N N h R SO2 N + N2
b)
or
R = alkyl, aryl 

+ _
h
c) RO C N N N RO C N + N 2
or
O  O
R = alkyl, aryl

d) RO C NH O SO2 NO2
_
O
RO C N + O SO2 NO2
base
_ O
(nosylate)
RO C N O SO2 NO2
O
MECHANISTIC ASPECTS OF NITRENE
CHEMISTRY
Cycloaddition - Observations

Liquid phase experiment

R R

_ H3C CH 3 N N
+
R N N N + C C h +
H H H3 C CH 3 H3 C H
H H H CH 3
cis trans
(predominant aziridine product) (minor aziridine product)

Point of Information: When an inert solvent is added to the reaction mixture, more trans-
product is obtained at the expense of the cis-product.
 MECHANISTIC ASPECTS OF NITRENE
CHEMISTRY
Cycloaddition

Explanation for Nitrene Cycloaddition: R R

R N R N N N

H H H H
singlet triplet C C spin C C
+ + H3C CH3 inversion H3 C CH3
H diradical
H H H
C C C C rotation
H3C CH3 H3 C CH3
ring R
closure N
cis product H CH3
R C C
+ H3 C
N H
trans product
H H ring closure
H3 C CH3
cis
 MECHANISTIC ASPECTS OF
NITRENE CHEMISTRY
Insertion - Observations
H
_ H N R
+
R N N N + CH3 CH 2 C CH2 CH2 CH3 CH3 CH 2 C CH 2 CH2 CH3
CH 2 Cl2
CH 3 CH3
R= C OC2 H5 (+) S-3-methylhexane (+) R-product
O

Method of Generation Conc. of Alkane Obs. rot. of prod. Retention of Config

o
R N3 100% +1.69 99%

o
R N3 1.2% +1.71 100%
h
o
R N3 26.8% +1.69 99%
h
o
R N3 100% +1.68 98%
h
EVIDENCE OF SINGLET NITRENE C-H
INSERTION SELECTIVITY
R N + alkane alkane insertion products
(singlet)

Alkane Relative reactivities

CH3 CH 3 CH 3 CH3 CH3 CH3

R N
H3C C C CH3 H3 C C C CH3 + H 3 C C C CH2 NH
H H H NH R H H R
67.0 : 1.0

H H H H H H
R N
H3 C C C CH3 H 3 C C C CH3 + H 3 C C C CH2 NH
H H H NH R H H R

9.0 : 1.0

Singlet nitrene C-H insertion selectivity: tertiary C-H > secondary C-H > primary C-H
 Advanced Organic Chemistry By
Bhal And Bhal.
 Textbook Of Organic Chemistry
By O.P.Agrwal.
 Organic Chemistry By
R.T.Morrison And R.N.Boyed