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 Physical Organic Chemistry

Chapter 1
Chemical Bonding and Structure

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 Goal
• Transition from VSEPR and VBT to MOT

- VSEPR: Valence Shell Electron Pair Repulsion

▪ All groups as far apart as possible

- VBT: Valence Bond Theory

▪ Lewis structures
▪ Hybridization
▪ Localized orbitals between nuclei

- MOT: Molecular Orbital Theory

▪ Combine AOs to make MOs
▪ Understand structure & reactivity (group orbitals)
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 Lewis Structures

 Focusses on bonds!
 Note: formal charges (mind the electronegativity)
 No insight into molecular shapes, structure and reactivity

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 Lewis Structures

 formal charges (mind the electronegativity)

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 VSEPR

 Focusses on shape and structure

dictated by steric repulsion
 In this model lone pairs are bigger
than bonded pairs
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 Methane - VSEPR
Molecular formula Lewis structure

CH4 Steric number = 4

Tetrahedral geometry

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 Methane - hybridisation (sp3)

s, spherical distribution of e density

p, linear, node at nucleus. 90 degree angles

Orbitals – mathematical description of the wave

function with positive and negative phasing.

Overall: gives probability of electron distribution

http://cwx.prenhall.com/petrucci/ 9
 Methane - hybridisation (4x sp3)

Add 4 H

Are all 4 C-H bonds the same?

http://cwx.prenhall.com/petrucci/ 10
 Hybridization
Method of adding and substracting atomic orbitals

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Hybridization & electronegativity

sp sp2 sp3

and hybridisation

 Electronegative element prefers

greater s character in its LP orbital
to keep the electrons to itself
 This places more p orbital character
in the bonds to H, which reduces
the H-X-H bonds. This effect is more
pronounced for O as it is more electronegative
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 Goal
• Transition from VSEPR and VBT to MOT

- VSEPR: Valence Shell Electron Pair Repulsion

▪ All groups as far apart as possible

- VBT: Valence Bond Theory

▪ Lewis structures
▪ Hybridization
▪ Localized orbitals between nuclei

- MOT: Molecular Orbital Theory

▪ Combine AOs to make MOs
▪ Understand structure & reactivity (group orbitals)
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 (Anti)Bonding
(de)stabilize

 Sigma & pi Bonds arise from

overlap of AOs
 MOT: creation of (anti)bonding orbitals via mixing
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 Overview
• VSEPR / Valence bond theory / Molecular Orbital theory

Group orbitals: Building larger:

 Methane  Ethane
 Ammonia  Ethylene
 Borane  Formaldehyde
 Water  Butadiene
 CH2  Benzene
 CH3+

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 Methane - Orbital theory
Atomic Orbitals?
How to combine to make MOs?
-lineair combinations of unhybridized atomic orbitals

Hydrogen
+ or –
+
Carbon
–

Two phases / signs per AO

Combine: In phase → constructive (bonding)
Out of phase → destructive (anti bonding)
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 Methane - Orbital theory
H C

Combine: In phase → constructive (bonding)

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 Methane - Orbital theory
H C

Combine: In phase → constructive (bonding)

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 Methane - Orbital theory
Energy levels?
Out of phase
→ destructive
→ anti bonding

Hund

In phase
→ constructive
→ bonding Aufbau
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 Methane - Orbital theory
Ionization Energies

2s
2p

Hund

In phase
→ constructive
→ bonding Aufbau
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 Qualitative Molecular Orbital Theory
1. Consider valence orbitals only
2. Form delocalized MOs as linear combinations of AOs
3. MOs must be symmetric or antisymmetric with respect to
symmetry operations:

Which structure has the highest symmetry? and why?

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 Qualitative Molecular Orbital Theory
1. Consider valence orbitals only
2. Form delocalized MOs as linear combinations of AOs
3. MOs must be symmetric or antisymmetric with respect to
symmetry operations:

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 Qualitative Molecular Orbital Theory
4. Compose MOs for structures of high symmetry first
5. Similar molecular structure → similar MOs (e.g., CH3 and NH3)
6. Total energy is sum of the MO energies of individual electrons
7. Two highest energy MOs of a given symmetry derive primarily
from different kinds of AOs, then mix the two MOs to form
hybrid orbitals.
8. When two orbitals interact, the lower energy orbital is
stabilized and the higher energy orbital is destabilized.
9. When two orbitals interact, the lower energy orbital mixes
into itself the higher energy one in a bonding way, the higher
energy orbital mixes into itself the lower energy one in an
antibonding way.
10. The smaller the initial energy gap between two interacting
orbitals, the stronger the mixing interaction.

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 Qualitative Molecular Orbital Theory
(QMOT)

11. The larger the overlap, the larger the interaction.

12. The more electronegative elements have lower energy AOs
13. Change in geometry gives change in the energy of a MO if
the geometry change leads to large changes in AO overlap

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 QMOT: CH3
Rule 4: Compose MOs for structures of high symmetry first

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 QMOT: CH3
Rule 4: Compose MOs for structures of high symmetry first

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 QMOT: CH3
Rules 2 and 3: Mix AOs (C: 2S, Px, Py, Pz and 3x H: 1S)

Anti-bonding

Non-bonding

Bonding

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 QMOT: CH3

Atomic Orbitals? How to combine?

Hydrogen

Carbon

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MH3 group orbital

2s

What happens upon distortion to tetrahedral?

2p

If two highest energy MOs

of a given symmetry (C3)
derive primarily from
different kinds of AOs,
then mix the two MOs
to form hybrid orbitals.
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 The Walsh diagram: pyramidal CH3
Rule 4: create orbitals for related but less symmetric structures
by systematic distortion

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 The Walsh diagram: pyramidal CH3
Rule 7: Two highest energy MOs of a given symmetry derive primarily
from different kinds of AOs, then mix the two MOs to form hybrid orbitals

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 Putting the electrons in (MH3 system)
Rule 5. Similar molecular structure → similar MOs (e.g., CH3 and NH3)
Example 1: BH3 (6 valence electrons) PLANAR

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 Putting the electrons in (MH3 system)
Rule 5. Similar molecular structure → similar MOs (e.g., CH3 and NH3)
Example 1: BH3 (6 valence electrons) PLANAR

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 Putting the electrons in (MH3 system)
Rule 5. Similar molecular structure → similar MOs (e.g., CH3 and NH3)
Example 2: NH3 (8 valence electrons) Pyramidal

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 Putting the electrons in (MH3 system)
Rule 5. Similar molecular structure → similar MOs (e.g., CH3 and NH3)
Example 2: NH3 (8 valence electrons) Pyramidal

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 Water (H2O) - Orbital theory
Atomic Orbitals? How to combine?

Hydrogen

Oxygen

Use the MH2 group orbitals!

(page 34) 36
Walsh Diagram (MH2 system)
Begin with linear geometry, distort to bent

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MH2 group orbital

2s

2p

If two highest energy MOs

of a given symmetry (C2)
derive primarily from
different kinds of AOs,
then mix the two MOs
to form hybrid orbitals.
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 Water (H2O) - Orbital theory

Use the MH2

HOMO group orbitals!

HOMO -1
B3LYP (6-31G*)

How do ?thevalence
many
Bending “lonepairs”
electrons
look like? does H2O
have?
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Putting electrons in (H2O)
H2O (8 valence electrons)

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 Walsh Diagram (:CH2 carbene system)
From linear geometry…

How many valence

electrons does :CH2
have?

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Walsh Diagram (:CH2 carbene system)
From linear geometry…

Spin state =½ + ½ = 1
Multiplicity Ms = 2S +1 = 3 (i.e., triplet state) 42
Walsh Diagram (:CH2 carbene system)
…to distorted

Spin state =½ - ½ = 0
Multiplicity Ms = 2S +1 = 1 (i.e., singlet state) 43
 Building larger molecules

• Combine the group orbitals

• Similar to combining atomic orbitals

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 Building larger molecules
Antibonding

Bonding
Pauli repulsion

Rule 8. When two orbitals interact, the lower energy orbital is

stabilized and the higher energy orbital is destabilized
Think of 2x NH3 (4e, no reaction) and NH3 + BH3 (2e, reaction) 45
 Building larger molecules
Electronegative
elements lower the
Energy of the AO.
Polarization!!
Larger coefficients!!

Rule 9. When two orbitals interact, the lower energy orbital mixes
into itself the higher energy one in a bonding way, the higher
energy orbital mixes into itself the lower energy one in an
antibonding way.
Think of a C=O group, HOMO mostly on O, LUMO mostly on C 46
 Building larger molecules

energy gap

Rule 10. The smaller the initial energy gap between two interacting
orbitals, the stronger the mixing interaction.

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Ethane - Orbital theory

Which orbitals
should we
consider?

Combine two MH3

group orbitals
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Ethane - Orbital theory

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Building larger molecules
Ethane

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 Building larger molecules
Ethane

Rule 11. The larger the overlap between interacting orbitals, the
larger the interaction.
s(CH3) and p(CH3) are mainly C-H and not C-C bonding!
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 Building larger molecules
Ethane

Consider the effect of rotation around the C-C bond (3 kcal/mol)

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 Ethylene - VSEPR
Molecular formula Lewis structure

H2CCH2 Steric number = 3

trigonal planar geometry

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Ethylene - Orbital theory

Which orbitals
should we
consider?

Combine two MH2

group orbitals
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Ethylene - Orbital theory

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H2C=CH2

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 Formaldehyde - VSEPR
Molecular formula Lewis structure

H2CO Steric number = 3

trigonal planar geometry

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 The Effects of Heteroatoms
H2C= O

• Formaldehyde and ethylene are isoelectronic:

• Same number of valence electrons
• Same type of valence orbitals

• Similar MOs can be expected

• Some perturbations introduced by electronegative oxygen

Rule 12. The more electronegative elements have lower energy

AOs (leading to polarization)
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Formaldehyde (CH2O) - orbital theory
Oxygen:

Which orbitals do we need?

• CH2 group orbitals
• s, px, py, pz orbitals from oxygen

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Formaldehyde (CH2O) - orbital theory
LUMO

HOMO

Notice the polarization

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 The Effects of Heteroatoms
H2C= O
LUMO
p* polarized
p*
towards C

HOMO
sign.C-H
bonding

p polarized p
towards O

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 The Effects of Heteroatoms
H2C= O
LUMO
p* polarized
towards C

HOMO
sign.C-H
bonding

p polarized
towards O

Nucleophiles will react at larger coefficient, thus C

matches with resonance structures from VBT

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 Even larger
 π orbitals of butadiene

 Combine HOMO/LUMO of two

ethylene molecules

 Building up nr. of nodes

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 Even larger

 π orbitals of
benzene

 Building up nr. of
nodes (from 2
allyls)

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 Carbenium ions
Example: CH3+ (6 valence electrons) PLANAR

Why is the order of stabilities for carbocations

3o>2o>1o>methyl?
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 Carbenium ions

Hyperconjugation p(CH3) and p-orbital mixing!

(VBT)
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