Structure and reactivity of organic molecule

Structural Effects
Effect of the structure on STABILITY and REACTIVITY of the
organic compound.
1. Electron Delocalization
A. pi electron delocalization
B. sigma (σ) electron delocalization / CH hyperconjugation
C. Lone pair delocalization
2. Inductive Effect
A. Electron Attracting or Withdrawing Inductive Effect
B. Electron Repelling or Donating Inductive Effect
3. Steric Effect
4. Angle Strain
5. Aromaticity
1. Electron Delocalization

• Electrons belonging to certain molecules are not attached to a particular

atom or bond in that molecule.
• These electrons are said to be "delocalized" because they do not have a
specific location (are not localized); they cannot be drawn in a simple Lewis
structure. Rather, they exist in orbitals that include several atoms and/or
bonds.
• You can imagine these orbitals as clouds surrounding parts of the
molecule.
• Delocalization gives molecules resonance stability
• The actual structure with delocalized electrons is called a resonance
hybrid.
A. Pi electron delocalization (Resonance)

• The delocalized electrons mainly come from a pi bond. Recognize that a

conjugated diene is actually a sp2 system, and will demonstrate resonance.
B. Sigma pi delocalization (CH hyperconjugation)

• Delocalized electrons come from a sp3 hybridized carbon.

• Alkyl substituents (having hydrogen on alpha carbon ) on carbon-carbon double
bond acts as electron donors to pi system- this electronic interaction is known as
hyperconjugation or no-bond resonance

No. of resonating structures = NO. of alpha Hydrogen + 1

C. Lone pair delocalization

• The delocalized electrons mainly come from a lone pair, most often from a
nitrogen or oxygen atom.
 VERY IMPORTANT POINT

The ability to be able to delocalise (spread out) charge via

resonance allows an assessment of

(i) the degree of ease of formation of the charged species,

(ii) the stability of the charged species

 The Resonance Arrow and its Physical Meaning
The resonance arrow is not an equilibrium arrow

O O
H3C H3C
O O

The resonance arrow shows only the distribution of electrons.

Thus, for the two degenerate structures above, the implication is that there is an even
distribution of the two electrons between the two oxygen atoms, at all times.

O
H3C
O
Experimentally it is found that both C-O bonds are the same length and are intermediate
in length between the C-O single and double bond, as are the C-C bonds in benzene.
General Structure that will Display Resonance of Charges and
Lone Pairs of Electrons

R 1 R3

R2 R4

R1 R3

R2
R4
Some Important Aromatic Resonance Structures
Nitro Group: An Electron Withdrawing Group

O O O O O O O O
N N N N

Canonical structurtes

O O
N
O O
N
Repels
E

Attracts E
 Methoxy Group: An Electron Donating Group

OMe OMe OMe OMe

Canonical structurtes
…Note in a reaction mechanism we would not show the lone pairs on the carbons
carrying the –ve charge…

OMe OMe OMe OMe

Canonical structurtes
These resonance structures allow us to rationalise (and
predict) reactivity

OMe

OMe OMe
Attracts
E E

Repels
E
Acidic compounds

• two resonance contributors can be drawn for the conjugate base, and the negative
charge can be delocalized (shared) over two oxygen atoms
• Ethoxide ion, by contrast, the negative charge is localized, or ‘locked’ on the single
oxygen
Basic compounds
Rank the compounds below from most acidic to least acidic, and explain your
reasoning

Out of four OH group, which OH protons is most acidic?

2. Inductive Effect

• An inductive effect is an electronic effect due to the polarization of σ bonds within

a molecule or ion.
• This is typically due to an electronegatvity difference between the atoms at either
end of the bond.
• The more electronegative atom, the more it pulls the electrons in the bond
towards itself creating some bond polarity
• Basis here is the polarity.
• Three considerations:
1). electronegativity, 2). bonding order and charge and 3). position within a
structure.
Electronegativity Values

H C N O F
2.1 2.5 3.0 3.5 4.0

Si P S Cl
1.8 2.1 2.4 3.0

Br
2.8

I
2.5
Bond Polarisation and Inductive Effects

-I Inductive Effects +I Inductive Effects

d+ d- d- d+
C F C H

d+ d- d- d+
C
-
Cl C CH3
d+ d- d- CH3
d+
C O C C CH3
CH3
Electron attracting or Withdrawing
Inductive Effect

• Has a Negative inductive effect (-I)

• Electrons are draw on towards atoms with:
• 1. Excess positive charges
• 2. Electronegative atoms
• 3. Atoms with increased electronegativity due to more electrons
Electron donating inductive effect
• Has a positive inductive effect (+I)
• Electrons are repelled by:
• 1. Less electronegative atoms (ex. C)
• 2. Negatively charged functional groups
Inductive Effects are Short Range
In Contrast to Resonance Effects

This proton is acidic

d+
H

d+
d+ d-
H3C CH CH2 Cl
d+
The polarised C-Cl bond transmits further
polarisation through the s-bond framework,

But effect drops off quickly…

 Important when considering
Inductive Effects and Carbocation Stability substitution reactions in part 4
of this course

LEAST MOST
STABLE STABLE

H CH3 CH3 CH3

C C C C
H H H H H3C H H3C CH3

Methyl Primary Secondary Tertiary

Carbocation Carbocation Carbocation Carbocation

Carbon atom is electron deficient (only has 6 electrons

in its outer valence). CH3
The methyl groups have +I inductive effects.
C
Thus, extra electron density is ‘pushed’ onto the
carbocation, which stabilises the carbocation. H3C CH3
 Common Substituents grouped according to
Resonance and Inductive effects

-R, -I +R, -I +R, +I

NO 2 F, Cl , Br , I CH3

C N OH , OR CH2 R

C OH , C NH 2 SH , SR CHR 2
O O NH 2 , NHR , NR 2 CR 3
C OR , C X
O C R , NH C R O- , S-
O O
O O
C H, C R
O O

CF3
3. Steric Effect

• Electrical instability caused by closing in of electron dense atoms. • Atoms in molecules

occupy certain amounts of space. If they are brought too close to each other, their electron
clouds may repel each other causing a steric strain that may affect the reactivity of the
molecule.
4. Angle Strain

• Electrical instability in atoms closing in with small angles in cyclic compounds.

• Atoms in cyclic molecules share a certain angle between each other. The ideal is
109.5 degrees. As the goes farther or lower than that, the repelling effect of
electrons on each other increases.
 5. Aromaticity
Criteria for Aromaticity

1. A compound must have an uninterrupted cyclic cloud of p electrons

above and below the plane of the molecule:

2. The p cloud must contain an odd number of pairs of p electrons,

or 4n + 2 (n = 0, 1, 2 …) total electrons.
3. Hϋckel’s Rule

• If the compound is cyclic,planar, fully conjugated & posses (4n

+2) π electrons, then it is an aromatic compound, n = 0 1 2 3
• If the compound is cyclic, planar, fully conjugated & posses 4n π
electrons, then it is an anti-aromatic compound.
where n is any integer like 1,2,3,……..
Monocyclic hydrocarbons with alternating single and
double bonds are called annulenes:

Cyclobutadiene and cyclooctatetraene are not aromatic,

because they have an even number of p electron pairs
Cyclooctatetraene is a stable compound because it is large
enough to form a tub shape, thereby removing degenerate
orbitals
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 not not
aromatic
aromatic aromatic

Cyclopentadiene does not have an uninterrupted ring of

p orbital-bearing atoms

Cyclopentadienyl cation has an even number of p

electron pairs

Cyclopentadienyl anion has an uninterrupted ring of p

orbital-bearing atoms and an odd number of p electron pairs
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The resonance hybrid shows that all the carbons in the
cyclopentadienyl anion are equivalent

Each carbon has exactly one-fifth of the negative charge

associated with the anion

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These compounds consist of fused benzene rings and are
aromatic:

Any compound consisting of fused benzene rings is

aromatic

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 Aromatic Heterocyclic Compounds
Heteroatom donates one Heteroatom donates two electrons
electron

A heterocyclic compound has ring atoms other than carbon

The heteroatom donates either one or two electrons to the 

system
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The Effect of Aromaticity on the pKa
Values of Some Compounds

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Why is the pKa of cyclopentadiene so much lower than
that of ethane?

The conjugate base is aromatic:

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Aromaticity influences chemical reactivity:

The cycloheptatrienyl cation is aromatic:

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