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Lecture 35 PDF

1. The document discusses molecular orbital theory and how σ and π orbitals are formed from the overlap of atomic orbitals. It explains how σ and π molecular orbitals are classified based on their symmetry. 2. Methods for constructing molecular orbitals are described, including using available valence orbitals from atoms. Frost-Musulin diagrams are introduced as a way to determine the relative energies of molecular orbitals for cyclic conjugated molecules. 3. Hückel's rule is summarized, stating that monocyclic planar compounds with (4n+2) π electrons will be aromatic and have closed shells of delocalized π electrons.

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123 views20 pages

Lecture 35 PDF

1. The document discusses molecular orbital theory and how σ and π orbitals are formed from the overlap of atomic orbitals. It explains how σ and π molecular orbitals are classified based on their symmetry. 2. Methods for constructing molecular orbitals are described, including using available valence orbitals from atoms. Frost-Musulin diagrams are introduced as a way to determine the relative energies of molecular orbitals for cyclic conjugated molecules. 3. Hückel's rule is summarized, stating that monocyclic planar compounds with (4n+2) π electrons will be aromatic and have closed shells of delocalized π electrons.

Uploaded by

Rachit Shah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry


II-Semester: AY 2018-19
Lecture 35 (12-04-2019)
BITS Pilani, Pilani Campus
Summary of Lecture 34
H H
H H
C C C C C C
Cl Cl
CH3 CH3

Resolution of Enantiomers:
Resolution: Separating enantiomers by
• Two methods:
– Chemical resolution
make environment chiral so that
– Chromatographic resolution enantiomers have different properties.

Relative and absolute configurations


CH3 CH2 CH2Cl
Cl Cl
Cl2
H Cl H H Cl
C 2H 5 C 2 H5 C2H5
(S)-2-chlorobutane Same relative configuration (R)-1,2-dichlorobutane
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Molecular Orbitals using p-Atomic Orbitals
According to molecular orbital theory, σ orbitals are built from all orbitals that have the
appropriate symmetry.
If we take molecular axis as Z-axis then Overlap of pz orbitals leads to σ and σ*

The bonding orbital is given the notation σg, where the g stands for gerade, or
symmetric around the bond axis and anti-bonding orbitalis given the notation σu,
where the u stands for ungerade, or asymmetric around the bond axis.
Overlap of 2px and 2py orbitals lead to a pair of π and a pair of π *
orbitals.

π-bonding orbitals are asymmetric about a center of symmetry or it is ungerade


and anti-bonding orbital is gerade, or symmetric about a center of symmetry.
Note that the designations of u or g do not correlate with bonding or anti-bonding.
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Construction of molecular orbitals
 Use of available valence orbitals from atoms
 Classify according to symmetry (σ/π) with respect to axis
 From Nσ AO’s build Nσ MOs for σ symmetry
 Similar Nπ MO’s of π -symmetry. These occur in degenerate pairs.
 In general, the energy of each type of orbitals increases with the number of
inter-nuclear nodes

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Construction of molecular orbitals

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π -Mos of conjugated Molecules

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π -Mos of cyclic conjugated: Frost-Musulin diagrams
Draw the molecular framework of a cyclic system of overlapping p-orbitals, making
sure you put an atom at the bottom. Atomic positions (positions of p-orbitals) then
map on to the energy level diagram!
Draw a horizontal line through the center of the circle and label MOs as
bonding, antibonding and nonbonding.
•MOs below the line are bonding, and lower in energy then p-orbitals from
which they are formed.
•MOs above the line are anti-bonding, and higher in energy then p-orbitals
from which they are formed.
•MOs on the line are non-bonding, and equal in energy to the p-orbitals from
which they are formed.

make sure to put a vertex


[that’s a pointy part]
down. This is important or
7 it won’t work. BITSPilani, Pilani Campus
Frost-Musulin diagrams of benzene

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π-Mos of Benzene

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π-Mos of Benzene

The relative energies of MOs for cyclic conjugated molecules can be


determined by Polygon Method of Predicting (Frost-Musulin diagrams).
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π -Mos of cyclic conjugated Molecules

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Hückel’s Rule: The (4n+2)p Electron Rule & MO
For monocyclic planar compounds in which each atom has a p orbital,
Hückel showed that compounds with (4n+2) p-electrons, where n = 0, 1,
2, 3 etc, would have closed shells of delocalised p electrons and should
show exceptional stability (high resonance energy “aromatic”). i.e.
planar monocycles with 2, 6, 10, 14….delocalised p electrons should be
“aromatic”.
For the compound to be aromatic, bonding MOs must be completely filled with
electrons, so the “magic numbers” for aromaticity fit Hückel’s 4n + 2 rule.

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Criteria for Aromaticity—Hückel’s Rule
Four structural criteria must be satisfied for a compound to be aromatic.
[1] A molecule must be cyclic.

[2] A molecule must be planar. All adjacent p orbitals must be aligned so that the 
electron density can be delocalized.

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Criteria for Aromaticity—Hückel’s Rule

[3] A molecule must be completely conjugated. Aromatic compounds must have a p


orbital on every atom.

[4] A molecule must satisfy Hückel’s rule, and contain a particular number (4n+2)
of  electrons.
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Aromatic compound with heteroatom
• Heterocycles containing oxygen, nitrogen or sulfur, can also be aromatic.
• With heteroatoms, we must determine whether the lone pair is localized on the
heteroatom or part of the delocalized  system.
• An example of an aromatic heterocycle are pyridine, pyrrole etc.

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Ions as Aromatic compound
Both negatively and positively charged ions can be aromatic if they possess all
the necessary elements.

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Non-benzenoid Aromatics
Annulenes: Hydrocarbons containing a single ring with alternating double and
single bonds are called annulenes. To name an annulene, indicate the number
of atoms in the ring (usually, the number of π electrons) in brackets and add
the word annulene.

[12]anuulene [16]anuulene
4n [14]anuulene 4n [18]anuulene
(anti-aromatic) 4n+2 (anti-aromatic ) aromatic
(aromatic )
[18]annulene is a planar, fully aromatic compound. The ring is just large enough that the
hydrogens sticking into the middle of the ring do not interact to twist the molecule out of
planarity.
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Non-benzenoid Aromatics
Azulene is one of the few non-benzenoids that appears to have significant
aromatic stabilization. It has a noticeable dipole moment (0.8 D).
It acts like a combination of cyclopentadienyl anion and cycloheptatrienyl cation.

In contrast, Pentalene and heptalene which posses fused five and seven membered
rings, respectively, are not stable but conjugate acid of heptalene is very stable,
reflecting the stability of resulting Tropylium cation.

Unstable
The large measured dipole moments and reduced barrier of
rotation of the unsymmetrical fulvalene (x) analog are
manifestations of aromatic stabilization.
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Chemical and Physical Properties of Conjugated Molecules
Delocalization means possibility of new orbital overlap and additional stabilization
of the system.
Delocalization has important effects on both the stability and chemical reactions of
this conjugated molecule.
Molecules with conjugated multiple bonds are generally more stable than
comparable molecules with unconjugated multiple bonds.
We can see this extra stability due to conjugation when we compare heats of
hydrogenation of related conjugated and unconjugated systems.
The extra stability (in terms of energy) gained through delocalization is called
delocalization energy or resonance energy.
-253 KJ/mol

-223 KJ/mol

-229 KJ/mol

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Aromatic vs. Unsaturated Compounds
• Unusual Stability: Based on heats of hydrogenation

• Unusual Reactions
Alkene + KMnO4  diol (addition) Alkene + Br2/CCl4  dibromide (addition)
Benzene + KMnO4  no reaction. Benzene + Br2/CCl4  no reaction.
Benzene (aromatic compounds) react with Br2 in presence of catalyst (FeBr3 etc.) to
form bromobenzene.
It’s a substitution reaction. Double bonds remain. Aromatic compounds behave
differently than unsaturated compounds.
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