BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 34
Dr. Ajay K. Sah
BITSPilani, Pilani Campus

Alkene Additions
H

H
H

Br

CH3
H

OH

CH3
H

HBr

H2O

H2O

CH3
H

Br
H

Regiochemistry
HO

Let us look at this

CH3
H

CH3

Br

Br2

H2
H

CH3
H

"HO" x 2

BrOH
HO
H

CH3
H

Br
H

OH

CH3
H
OH

CH3
H

Is there a universal
mechanism?

* (p)
* (p)
LUMO

(p)

(p)
* (s)
(s)

Diatomic MOs
for Br2

HOMO

A
Br2

Side on Br2 addition is symmetry forbidden.

End on addition is allowed.

*
A

LUMO
LUMO

C2H4

HOMO
HOMO

A
Br2

The addition of halogens (Br2, Cl2) to alkenes.

Stereochemistry.
Br
Br
Br

Anti-addition

Br
H

Br

Br

Br

Br
Br
Br

Br
H

Br

Br
5

The addition of halogens (Br2, Cl2) to alkenes.

Stereochemistry.
Br
Br

Anti-addition

Br
H

Br

Br

+ R

Br

Br

Br

Br

Br
R Br

S
S

Br
6

The addition of halogens (Br2, Cl2) to alkenes.

Stereochemistry.
Br
Br

Anti-addition

Br
H

Br

Br

+
Br

Br
Br

Br

Br

Br

Br

Br
H

Br
Br

Br
7

The addition of halogens (Br2, Cl2) to alkenes.

Stereochemistry.

Anti-addition

Br2

Br

+ R

Br

Br

trans

Br2

cis

Br

Br

Br
R Br

S
S

Br
8

The addition of Br2 in presence of H2O to alkenes.

Regiochemistry and Stereochemistry.
Anti-addition

Br2

Br

H2 O
OH

The addition of Br2/H2O to alkenes.

Regiochemistry and Stereochemistry.

Anti-addition

Br
Br
Br

H O

Br

Br

Br

H
H

O H

O H

10

The addition of Br2/H2O to alkenes.

Regiochemistry and Stereochemistry.

Anti-addition

Br
Br
Br

H O

Br

Br

Br

H
H
H

O H

O H

H
Br

H
H
H

Br

H
H

11

The addition of BrOH to alkenes.

Regiochemistry and Stereochemistry.

Anti-addition

Br
Br
Br

H Br

H O

Br

Br

H
H

O H

O H

weaker bond
12

Br-Br

Br

Br

H2O

O
H

Br

Br

Br

equal

2.06

Bromonium ion is symmetrical

13

Br

Br-Br

H3C

H2O

H3C

H3C

H3C

O
H

Br

Br

Br

Br

H3C

H3C
more important

2.06

2.17

2.03

14

Predict the product of the following reaction.

CH3
H

Br2
H2O

CH3
OH
H
Br

Br
CH3
OH
H

eight isomers possible!

only two are observed!!

15

CH3
H

CH3
OH

Br2

H
Br

H2O

CH3

OH
CH3
Br
H

CH3

Br
H

Br
H

16

Alkene Additions
H
H

CH3
H

CH3
H

Br

Br

OH

CH3
H

HBr

H2O

Regiochemistry
HO

CH3
H

Br

Br2

Now, let us look at this

H2O

CH3

H2
H

CH3
H

"HO" x 2

BrOH
HO
H

CH3
H

Br
H

OH

CH3
H
OH

CH3
H

Is there a universal
mechanism?

17

Reaction Mechanisms for Hydrogenation

How do the atoms of the reactant molecules
rearrange to form the product molecules?

H2 + CH2=CH2

CH3CH3

18

But first. Do we expect the reaction to occur?

Look at the thermodynamics.
Gr= products - reactants = -100 kJ/mol

Gf=0.0

Gf=+68 kJ/mol

?
Gf=-32 kJ/mol
19

Mechanism 1

H2 + CH2=CH2

CH3CH3

20

Mechanism 2

H2 + CH2=CH2

CH3CH3

21

Mechanism 3

H2 + CH2=CH2

CH3CH3

But as we will see this

close to correct for Br2

22

It looks good. What is wrong with this mechanism?

H
H

H
H

C
H

Mechanism 2

H
C
H

H2 + CH2=CH2

Examine
the M.O.s

CH3CH3

23

*
A

LUMO

LUMO

H2

C2H4

HOMO
HOMO

24

S (symmetric with
respect to reflection)

*
A

LUMO

A (asymmetric with
respect to reflection)
It has a node.

A-S Wrong Symmetry

No Interaction
HOMO

25

*
A

LUMO

LUMO

HOMO
HOMO

26

A-S Wrong Symmetry

No Interaction

LUMO

This reaction path

is forbidden by orbital
symmetry
HOMO

27

*
A

LUMO
LUMO

The direct reaction

of H2 and C2H4
is forbidden by orbital
symmetry

HOMO
HOMO

28

Energy

Gr = -100 kJ/mol
G

reactants
H2 + C2H4
0 + 68 kJ

Forbidden Reaction
G is too high
We need a
catalyst!

-100 kJ

C2H6
-32 kJ
products

Reaction Coordinate
29

What is a catalyst?
An added component that changes the
reaction mechanism to one with a lower
energy pathway. A lower G

The catalyst is neither produced or

destroyed during the reaction. It does
not change G of the reaction. It does
not change Keq of the reaction.
A catalyst can be simple like H+ or a metal
ion or it can be complex like an enzyme.
30

The platinum metals are often used in catalysis

They have partly filled d orbitals and empty s or p orbitals.
This means they can act as either an acid or a base.

31

Can H2 bind to a transition metal?

5p
orbital
S

LUMO

LUMO

A-A Allowed

4d
orbital
A

The reaction of H2
and a Ru ion is allowed
by orbital symmetry

S-S Allowed

HOMO

Ruthenium ion

HOMO

H2

32

Can C2H4 bind to a transition metal?

5p
orbital
S

LUMO

A-A Allowed
S-S Allowed

4d
orbital
A

HOMO

Ruthenium atom

LUMO

HOMO

S
33

Can C2H4 bind to a transition metal?

5p
orbital

LUMO

Symmetry
Allowed
4d
orbital
A

HOMO

Ruthenium atom

LUMO

HOMO

S
34

H-H
H2 + CH2-CH
=CH2

Ru

Catalyst
CH3CH3

CH3CH3
After the reaction
the catalyst is unchanged
and ready to go again.
35

Catalytic Hydrogenation:
Heterogeneous

C
H
H

Pt or Pd surface

36

H2 / Pd

C
H

C
H

syn or cis
addition

Both hydrogens add to the

same face of the alkene

C
H

C
H

Pt or Pd surface

37

Pd

H
C

H2/Pd
+ H

H
C C

HH

HH
both hydrogens add to the
same face of the alkene

CH3

H CH
3
H

H CH
3
H

H2

and

Pd
H

Stereochemistry of
hydrogenation is cis or syn.

H CH
3
H

not
H

38

Energy

H H

Symmetry forbidden
High energy
C C
Pd

reactants
Gr

H
H

Catalyzed pathway
Symmetry allowed
Lower energy

products
Reaction Coordinate
39

CH3

H2

CH3
CH
CH3 3

Pt

H
CH3

or

CH3

minor

Pt

H2/Pt

major

CH3

isomerization

equilibrium

CH3

CH3

H
CH3

CH3

H
Pt
H

H
CH3

H
H

40

Pericyclic Reactions

Electrocyclic and cycloaddition reactions

41

Pericyclic Reaction I

An intramolecular reaction in which a new s

bond is formed between the ends of a
conjugated p system

Electrocyclic Reactions Are Reversible

Pericyclic Reaction II

Two different p bond-containing molecules

react to form a cyclic compound

Pericyclic Reaction III

A s bond is broken in the reactant, a new s

bond is formed in the product, and the p bonds
rearrange

Pericyclic Reaction III

Pericyclic Reaction
The electrocyclic reactions and sigmatropic
rearrangements are intramolecular reactions
The cycloaddition reactions
intermolecular reactions

are

usually

Common features among the three pericyclic

reactions

are concerted reactions

are highly stereoselective

are not affected by catalysts

Pericyclic Reaction
The configuration of the product formed
depends on:

the configuration of the reactant

the number of conjugated double bonds or
pairs of electrons in the reacting system
whether the reaction is a thermal or a
photochemical reaction

Electrocyclic Reactions
1. Require heat or light only for initiation
2. No radical or ionic intermediates
3. Single concerted step involving a cyclic
transition state
4. Stereospecific reactions

Woodward & Hoffmann, Fukui and others

49

A Molecular Orbital Description of Ethane

50

A Molecular Orbital Description of 1,3-butadiene

(LUMO)

(LUMO) (HOMO)

(HOMO)

51

A Molecular Orbital Description of 1,3,5-hexatriene

52

53

54

An electrocyclic reaction is completely stereoselective

55

An electrocyclic reaction is completely stereoselective

56

Summary of Pericyclic Reaction

57