Welcome to IIT Bombay

and
CH 105
CH 105 – Organic Chemistry
Dr. Nandita Madhavan (nanditam@iitb.ac.in)
Office – Room 426, Chemistry
Phone – 7164

Please e-mail/come to my office to discuss doubts!

Your TAs are: Dashrath, Narendra, Praveen

and Sameer
 Course Content

• Huckel Theory for Conjugated Systems

• Stereochemistry

• Conformational Analysis

• Chemistry of Carbonyl Compounds

 Course Resources
Course Websites –
• moodle.iitb.ac.in
• Google classroom – Class code vq5ns19
Please register as we can have more one on one
interactions outside class

Text Books-

1. K. P. C. Vollhardt & N. E. Schore, ‘Organic Chemistry’. Structure and

Function’, Freeman Press, 5th Edition

2. Organic Chemistry, Clayden, Green, Warren and Wothers, Oxford

University Press.
 Course Evaluation
CH105 - Organic + Inorganic (one grade)

Organic: One Exam (50% Weightage)

Tutorials: 4 Tutorials covering topics covered in class

Tutorials are not counted to your grade

BUT

Useful for Self Evaluation, Clarification of Concepts, Practice

Interactive Lectures vs. Traditional Lectures
What does research say?

In Red – Lecture mode

In Green – Activity based approaches

Learning gain
Feel Free to Ask Questions in Class
“ No question is a silly question”
 Part - I
Huckel Theory for
Conjugated Systems

Slide content courtesy of -

Prof. R.B. Sunoj, IIT Bombay
Prof. Pradeepkumar P. I., IIT Bombay
Prof. S. J. Gharpure, IIT Bombay
Prof. K. M. Muraleedharan, IIT Madras
Conjugated/Aromatic Systems – Special?
Conjugated Systems Aromatic Compounds
Field Effect Transistors

Pentacene

OLEDs

Kevlar Tamoxifen
(Anticancer drug)
Image source: Google Images
 Thinking Time!!
Understanding Reactivity/Properties
1.39 Å 1.57 Å
1.39 Å Can this be
1.34 Å
explained by
Benzene Cyclobutadiene resonance
theory?
Aromatic, highly stable Highly unstable

Conductivity increases
However the central rings also show increased diene character???

Model better than resonance theory required !!!

 Learning Outcomes

At the end of this module you should be able to….

• Construct π – molecular orbitals for cyclic and
acyclic molecules

• Explain the reactivity of molecules and reaction

outcomes based on MO Theory
 Molecular Orbital Theory
Molecular Bonds – formed when two atoms are
brought from infinity close to each other
Molecular orbitals - obtained by combining the atomic
orbitals (AO) on the atoms
How do the AOs combine?
Think of the wave nature of electrons
MO2 Destructive (higher energy)

AO AO

MO1 Constructive (lower energy)

Energy
 Examples of Mixing

σ σ* Rows A & B
Axial overlap
σ MO
σ σ*

Row C
Lateral overlap
π π* π MO
Column A Column B
Constructive Destructive
Bonding MO Antibonding MO
 More on σ Orbitals

σ
• No nodes along the internuclear axis (Ignore AO nodes
e.g. of p orbital)

• Symmetric along the axis

Class tomorrow @ 8:30 am
LA 201
 Recap
How do the AOs combine?
Think of the wave nature of electrons
MO2 Destructive (higher energy)
(ψ1 = c1Ø1 - c2Ø2)

AO AO

MO1 Constructive (lower energy)

Energy
(ψ1 = c1Ø1 + c2Ø2)

• Remember the orbitals tell us the probability of finding the electrons

• n AOs will give you n MOs and each MO can accommodate only 2 electrons
• Do not confuse stability of the molecule with energy of MO. The electron
filling is important for that
Types of Orbitals – Ethylene (C=C)

s*
Antibonding MO
ABMO
p*

p
Bonding MO
BMO
s

A simplified picture
Can this be simplified further?
 Ethylene – Simplified MO picture
The σ – framework neglected as it is in the nodal plane of the
p atomic orbitals
Phase inversion
(node)

Qualitative Picture – Hückel’s MO

 Calculating Energies of MOs
Energy of each ith MO given by

EiMO = α + mjβ mj = 2 [Cos (jπ/n+1)]

Coulomb Resonance n = no: of carbon atoms

Integral Integral j = 1 to n
Coulomb integral – refers to energy of an electron in the field of its
own nucleus , [can be taken as valence state ionization potential]

Resonance integral - refers to energy of an electron in the field of the

neighboring nucleus , [can be taken as the interaction between
neighboring atomic orbitals]
Note: α and β are negative by definition
The α and β are not calculated as numerical values, but the energies are
expressed in terms of these quantities
 Ethylene – Energies of MOs

E2 = α - β

E1 = α + β

Total Energy = Σ (ne-i  Ei); ne- = no. of electrons

For Ethylene = 2(α + β) = 2α + 2β
 Applying to Larger Conjugated Systems
Molecular Orbital Picture
Let us look at the π-bonding interactions closely
The σ – framework neglected as it is in the nodal plane

interact π/ MOs

n n

Qualitative Picture – Hückel’s MO

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
 Activity

Draw the MOs of butadiene

 Butadiene MOs

Ψ4 = c1φ1 - c2φ2 + c3φ3 - c4φ4

E4 = a - 1.62b

Write the
wave equation Ψ3 = c1φ1 - c2φ2 - c3φ3 + c4φ4
for each MO LUMO E3 = a - 0.62b
Energy

Write the Ψ2 = c1φ1 + c2φ2 - c3φ3 - c4φ4

energy for E2 = a + 0.62b
HOMO
each MO
Ψ1 = c1φ1 + c2φ2 + c3φ3 + c4φ4
E1 = a + 1.62b
 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
 A Small Activity

• Please get your smartphones/Laptops out

• If you don’t have one please share with
your neighbour

• Go to www.menti.com –
• Use code 27 12 75
Happy anwering 
 Activity
Draw the MOs for an allylic cation