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Lecture6 MO2

The document discusses the molecular orbitals (MOs) of acyclic conjugated polyenes, detailing the arrangement of bonding, antibonding, and non-bonding MOs based on the number of nodes. It also covers the MOs of specific compounds like butadiene and hexatriene, highlighting patterns and energy levels. Additionally, it explains the significance of orbital energies in organic reactions, including nucleophilic and electrophilic behavior, and the mechanisms of SN1 and SN2 reactions.

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Brian Mackwan
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7 views15 pages

Lecture6 MO2

The document discusses the molecular orbitals (MOs) of acyclic conjugated polyenes, detailing the arrangement of bonding, antibonding, and non-bonding MOs based on the number of nodes. It also covers the MOs of specific compounds like butadiene and hexatriene, highlighting patterns and energy levels. Additionally, it explains the significance of orbital energies in organic reactions, including nucleophilic and electrophilic behavior, and the mechanisms of SN1 and SN2 reactions.

Uploaded by

Brian Mackwan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Recap - MO Construction Acyclic Conjugated Polyenes

antibonding MOs
Energy

n AO Non bonding

bonding MOs

Lowest energy MO 0 nodes


next MO 1 node
nth MO (n-1) nodes
The nodes are placed symmetrically
When n is even – n/2 bonding and n/2 antibonding MOs exist
When n is odd – (n-1)/2 bonding, 1 non-bonding and (n-1)/2 antibonding MOs exist
Butadiene MOs

Ψ4 = c1φ1 - c2φ2 + c3φ3 - c4φ4

The nodes Ψ3 = c1φ1 - c2φ2 - c3φ3 + c4φ4


are placed LUMO
Energy

symmetri-
cally

Ψ2 = c1φ1 + c2φ2 - c3φ3 - c4φ4


HOMO

Ψ1 = c1φ1 + c2φ2 + c3φ3 + c4φ4


Activity
Draw the MOs for
hexatriene
A Small Activity

• Go to www.menti.com –
• Use code 2278 5484
Happy answering ☺
MOs of Hexatriene
ψ6

ψ5

ψ4
Energy

LUMO

ψ3
HOMO
ψ2

ψ1
MOs – See any patterns?
ψ6
ψ4

ψ2 ψ5

LUMO ψ3
ψ4
LUMO
LUMO
Energy

ψ3
ψ2
HOMO
ψ1 ψ2
HOMO
HOMO ψ1
ψ1

2p 4p 6p
MOs of Larger Conjugated Polyenes
• The lowest energy orbital is always symmetric with
respect to the principal mirror plane

• The energy of the MO increases as the no: of nodes


increases
Eg. ψ1 - 0 nodes
ψ2 - 1 node
ψn - n-1 nodes
Again: Remember to ignore the nodes of the AO

• When you draw MOs place the nodes symmetrically


Draw the MOs of Allyl Cation

8
MOs of Allyl System

ψ3
LUMO LUMO
Antibonding
Energy

ψ2
LUMO
Non-bonding HOMO HOMO

ψ1

HOMO
Bonding 4e⁻
2e⁻ 3e⁻
Cation Radical Anion

The nodes are placed symmetrically


Summary: Acyclic Conjugated Systems
Broad Classification: Organic Reactions
▪ Polar Mechanism

E+ + Nu_ E Nu

▪ Radical Mechanism

A
. B
. A B
+

▪ Concerted Reactions
All the bonding changes occur at the same time and in a single
step – No intermediates involved !
Significance of Orbital Energies
A process that takes one stable molecular configuration (or set
of nuclei and occupied and unoccupied orbitals) to another
stable molecular configuration via unstable configurations

Transfer - electron rich to electron poor


Nucleophiles - Higher energy filled orbitals (Ready to donate
electrons to suitable electrophiles)
e.g., NH3 lone pair of electrons responsible for its nucleophilic
nature is its nonbonding MO

Electrophiles- lower energy unfilled orbitals


H
e.g., empty nonbonding MO in BF3 or CH3+
H

H
Common HOMO-LUMO Combinations
HOMO possibilities LUMO possibilities

Filled Unfilled

 *
π π*

n (non-bonding) n (nonbonding)
Explanation of Reactions Through Molecular Orbitals
SN1 Reaction – Attack from both sides of carbocation ok

(nBr)2 (nC)0

n
SN2 Reaction – backside attack only possible

*
(nO)2 (σ*C-Br )0
Rotational Barrier in Ethane
Barrier of 3 kcal mol-1 due to steric and electronic effects

Transition state Most stable rotamer


is eclipsed is staggered

15

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