Halogenation

σ* (p)
π* (p)
LUMO

σ (p)
π (p)

σ* (s)
σ (s) HOMO

Diatomic MOs for Br2 A

Br2
 Side on Br2 addition is symmetry forbidden.
End on addition is allowed.

LUMO
π* S
A LUMO

C2H4

HOMO
π HOMO A
S
Br2
The addition of halogens (Br2, Cl2) to alkenes
Stereochemistry. Anti-addition

Br
Br Br

Br

+
Br

Br
The addition of halogens (Br2, Cl2) to alkenes.
Stereochemistry. Anti-addition

Br Br
Br Br
Br H Br

H Br

Br +
Br H Br
Br
Br

H Br
 Br
Br Br

⊕
Br


⊕
 Br
H Br

H
Br
H Br

H
The addition of halogens (Br2, Cl2) to alkenes.
Stereochemistry. Anti-addition

Br
Br Br Br
Br H Br S + R
R S
H Br Br

Br
Br Br
H Br Br
Br S
R R Br +
H Br
S
The addition of halogens (Br2, Cl2) to alkenes.
Stereochemistry. Anti-addition
H

Br2 Br
Br
Br
Br H
Br

H
lower Br
Br2 H HH energy TS
H H H
C C
H H
H H Br H
anti addition Br
chair Br Br
higher
H HH energy TS
H H H
C C H H
H
H Br
Br Br
anti addition
twist-boat
The addition of Br2 in presence of H2O to alkenes.
Regiochemistry and Stereochemistry. Anti-addition

Br
Br2
H2O
OH

Br
Br H O Br Br
Br H Br H
H
O H O H
H
H
weaker
bond
 Br
Br H O Br Br
Br H Br H
H
O H O H
H
H
H Br
H
H

H Br
H
H
 Br-Br Br Br

H2O
H O
H

Br Br Br

equal

2.06Å Bromonium ion is symmetrical

 Br Br
Br-Br H3C

H2O
H3C O
H3C H
H

Br Br Br

H3C H3C H3C

more important

2.17Å 2.03Å
2.06Å
Predict the product of the following reaction.

CH3 CH3 Br
Br2 OH CH3
+
H 2O H OH
H
Br H

eight isomers possible!

only two are observed!!
CH3 CH3 OH
Br2 OH CH3
+
H H 2O H Br
Br H

CH3
CH3
Br
Br
H
H
Hydrogenation
Reaction Mechanisms for Hydrogenation

How do the atoms of the reactant molecules

rearrange to form the product molecules?

H2 + CH2=CH2 CH3CH3

?
But first. Do we expect the reaction to occur?

Look at the thermodynamics.

∆Gr°= Σproducts - Σreactants = -100 kJ/mol

∆Gf°=0.0
?

∆Gf°=+68 kJ/mol ∆Gf°=-32 kJ/mol

Mechanism 1

H2 + CH2=CH2 CH3CH3
Mechanism 2

H2 + CH2=CH2 CH3CH3
Mechanism 3

H2 + CH2=CH2 CH3CH3
It looks good. What is wrong with this mechanism?
H H Mechanism 2
H H
H
C C
H C C Examine
H H
H H H H the M.O.s

H2 + CH2=CH2 CH3CH3
 LUMO
σ*
π* A
A LUMO

H2
C2H4

π
S
HOMO
σ
HOMO S
 S (symmetric with
respect to reflection)

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

A-S Wrong Symmetry

No Interaction σ
HOMO S
 LUMO
σ*
π* A
A LUMO

π
S
HOMO
σ
HOMO S
 A-S Wrong Symmetry
No Interaction
LUMO
σ*
A

This reaction path

is forbidden by orbital
symmetry
π HOMO
S
 LUMO
σ*
π* A
A LUMO

The direct reaction of H2 and

C2H4 is forbidden by orbital
symmetry

π
S
HOMO
σ
HOMO S
Energy
∆Gr = -100 kJ/mol

Forbidden Reaction
∆G‡ ∆G‡ is too high

We need a
reactants catalyst!
H2 + C2H4
-100 kJ C2H6
0 + 68 kJ
-32 kJ
products
Reaction Coordinate
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.
The platinum metals are often used in catalysis
They have filled d orbitals and empty s or p orbitals.
This means they can act as either an acid or a base.
 Can H2 bind to a transition metal?

5p LUMO
orbital LUMO A
S A-A Allowed
The reaction of H2
and a Ru ion is allowed
by orbital symmetry

4d
orbital S-S Allowed
HOMO
A
σ
Ruthenium ion HOMO S
H2
Can C2H4 bind to a transition metal?

5p
orbital LUMO
S LUMO
A-A Allowed
S-S Allowed
Symmetry A
Allowed

4d
orbital
A HOMO
HOMO
Ruthenium atom S
 Catalyst
Ru
H2 + CH2=CH2 CH3CH3
H
H H + Ru Ru H2C CH2
H

H
CH2
Catalyst ready to Ru
be used again H CH2

H H2
Ru + H3C CH3 C
Ru
product CH2
H
 Catalyst
Ru
H-H
H2 + CH
CH22=CH
-CH22 CH3CH3

H H

CH
CH
CH23CH23
After the reaction
the catalyst is unchanged
and ready to go again.
Catalytic Hydrogenation: Heterogeneous

C C H H

C
H C

H H

Pt or Pd surface
 H2 / Pd
C C C C
H H
syn or cis
Both hydrogens add to the addition
same face of the alkene

C C
H C H C
H

Pt or Pd surface
 Pd
H H H2/Pd H H H H

C C + H H C C H C C H
H H HH HH H H
both hydrogens add to the
same face of the alkene
CH3 H CH H CH
H 3
H 3
H2
and
Pd
H H H
H CH
H 3

Stereochemistry of not
hydrogenation is cis or syn.
H
 H H
Energy Symmetry forbidden
C C High energy

Pd

∆G‡ H
H H
H
C C
∆G‡ H H

Catalyzed pathway
reactants
Symmetry allowed
∆Gr Lower energy

products
Reaction Coordinate
 Simmons-Smith Reaction

• The Simmons-Smith reaction is considered the

best way to carry out a cyclopropanation reaction.

• The reaction uses iodomethyl zinc iodide

(ICH2ZnI) as the source of the third carbon.

• This reagent, known as the Simmons-Smith

reagent, is not a carbene but it reacts like it so it is
called a carbenoid.