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.
States of Carbenes and Nitrenes

 Singlet state: carbocation-like in nature,

trigonal planar geometry, electrophilic
character
 Triplet state: diradical-like in nature,
linear geometry
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:
_ CH 3
+
CH2 N N + CH3 CH 2 CH 2 CH 2 CH 3 h CH3 (CH2 )4 CH 3 + CH3 CH CH2 CH2 CH3
(I) (II)
~49% ~34%
CH 3
+ CH3 CH2 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
 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
 Explanation of Nitrene Insertion

 Observed rotation is independent of chiral alkane

concentration.
 At less than 100% chiral alkane concentration (more
inert solvent present), more triplet nitrene is formed at
the expense of initially produced singlet nitrene..
nitrene.
 The fact that higher concentration of triplet nitrene does
not affect the observed rotation of chiral product is
indicative of the inability of the triplet species to insert
into alkyl C-H bonds.
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
 Summary of Carbene/Nitrene
Chemistry
 Singlet carbenes and singlet nitrenes add to C=C bonds
in a one-step, stereospecific manner.
 Triplet carbenes and triplet nitrenes add to C=C bonds
in a two-step, non-stereospecific manner.
 Singlet carbenes insert into alkyl C-H bonds randomly,
whereas singlet nitrenes do so selectively. Both singlet
species insert into alkyl C-H bonds with retention of
configuration.
 Triplet carbenes insert into alkyl C-H bonds selectively,
but not stereospecifically.
 Triplet nitrenes do not insert into alkyl C-H bonds.