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Carbenes - 1

The document provides an overview of carbenes, including their formation, properties, and key reactions. It explains the distinction between singlet and triplet states of carbenes and outlines various methods for generating them. Students are expected to understand the stability of carbenes, recognize their formation reactions, and be able to write mechanisms for these reactions.

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arimaharajh
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65 views14 pages

Carbenes - 1

The document provides an overview of carbenes, including their formation, properties, and key reactions. It explains the distinction between singlet and triplet states of carbenes and outlines various methods for generating them. Students are expected to understand the stability of carbenes, recognize their formation reactions, and be able to write mechanisms for these reactions.

Uploaded by

arimaharajh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd

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.

1
Carbenes are a family of organic
R C
molecules composed of a neutral
divalent carbon atom with a sextet of
2
electrons and two substituents.
R
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
p

px 

px

Triplet
Singlet
sp-hybridized
sp2-hybridized
H Cl R
R
B C
C C N C
R B R
H Cl R N R
methylene dichlorocarbene R
R
diborocarbene
diaminocarbenes

R
N C
N
R
cyclic diaminocarbenes
Formation reactions of carbenes:
• Diazoalkanes
hv or heat
R2C N N R2C N N R2C + N2

• Sulfonylhydrazones

Base
R2C N NH R2C N N R2C N N
SO2Ar SO2Ar

• Halides

Cl Cl
Base alpha-elimination
H C C Cl2C + Cl
Cl Cl
Cl Cl
GENERATION OF CARBENES:

(1) a-ELIMINATION OF HX OR X2 FROM AN ORGANIC HALIDE

X
- X, -Y
C C:
Y
a-ELIMINATION OF N2 FROM DIAZO-COMPOUNDS

R1 + _ R1
 or h
C N N C: + N2
or [M]
R2 R2
a-Carbonyl diazo-compounds - Important
precursors of a-carbonyl carbenes:
+ _
xs. CH2=N=N + _
R-COCl R-CO-CH=N=N
(Diazomethane)
_
+ _ +
CH2=N=N CH2-NN

_ + +
R-COCl + CH2-NN R-CO-CH2-NN + Cl-

+ + _
R-CO-CH–NN R-CO-CH=N=N + H+
H

_ +
CH2-NN + HCl CH3Cl + N2
H H
R C + _ R C +
C N C N
N _ N
O O

-Carbonyl Diazonium
diazo-compound enolate

H H
R C + , [Rh] R C
C N C
_ N - N2
O O
Diazonium -Carbonyl carbene
enolate
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

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