CHM 235-M.

T BAKER

Inductive Effect on Stability of Molecules

The charge on a given atom and the charge on a group bonded to the atom play a strong part when
determining the stability of the resulting molecule as per the inductive effect. An example of this
can be observed when a group displaying the -I effect is bonded to a positively charged atom and
the positive charge on the resulting molecule is amplified, reducing its stability. On the other hand,
when a negatively charged atom is introduced to a group displaying a -I effect, the charge disparity
is somewhat quenched and the resulting molecule would be stable as per the inductive effect. When
a group displaying the -I effect is bonded to a molecule, the electron density of the resulting
molecule effectively reduces, making it more likely to accept electrons and thereby increasing the
acidity of the molecule. When a +I group attaches itself to a molecule, there is an increase in the
electron density of the molecule. This increases the basicity of the molecule since it is now more
capable of donating electrons.

Electromeric effect
The electromeric effect is an intramolecular movement of electrons from a pi bond to another atom
in the molecule, due to attack by a reagent. It is temporary and reversible.
There are two distinct types of electromeric effects:
(i) Positive Electromeric effect (+E effect): In this effect the -electrons of the multiple bond are
transferred to that atom to which the reagent gets attached. For example:

(ii) Negative Electromeric Effect (-E effect): In this effect the -electrons of the multiple bond are
transferred to that atom to which the attacking reagents do not get attached. For example:

1
DIFFERENCES BETWEEN INUCTIVE AND ELECTROMERIC EFFECTS

A tabular column highlighting the key differences between the electromeric and the inductive
effects can be found below:

Inductive Effect Electromeric Effect

Works on sigma bonds Works on pi bonds

The inductive effect is permanent The electromeric effect is a temporary effect
It doesn’t require any attacking reagent An electrophilic attacking reagent is required
for this effect to arise.

Resonance Effect

Resonance is the polarity induced in a molecule by the interaction of a lone pair of electrons with
a pi bond or the interaction of two pi bonds in nearby atoms. It is the withdrawal or releasing effect
of electrons attributed to a specific substituent through the delocalization of π or pi-electrons,
which can be seen by drawing different canonical structures, is known as a resonance effect.

Sometimes, there are several correct Lewis structures for a given molecule. Ozone is one example.
The compound is a chain of three oxygen atoms, and minimizing the charges while giving each
atom an octet of electrons requires that the central oxygen atom form a single bond with one
terminal oxygen and a double bond with the other terminal oxygen. When drawing the Lewis
structure, the choice of placement for the double bond is arbitrary, and either choice is equally
correct. The multiple correct ways of drawing the Lewis structure are called the resonance forms.

Based on the resonance forms, a beginning chemistry student might wonder if ozone has bonds of
two different lengths, since single bonds are generally longer than double bonds. However, the
ozone molecule is perfectly symmetrical, with bonds that are the same length. None of the
resonance forms represent the true structure of the molecule. Rather, the negative charge of the
electrons that would form a double bond are delocalized, or distributed evenly across the three
oxygen atoms. The true structure is a composite, with bonds shorter than what would be expected
for single bonds, but longer than the expected double bonds. Thus for the two structures (I and II)

2
shown above constitute the canonical structures or resonance structures and their hybrid (i.e. the
III structure) represents the structure of more accurately. Resonance is represented by a double-
headed arrow between the resonance structures, as illustrated below.

The resonance hybrid is more stable than its canonical forms, i.e. the actual compound (hybrid) is
at a lower energy state than its canonical forms. Resonance stability increases with increased
number of resonance structures. The difference in the experimental and calculated energies is the
amount of energy by which the compound is stable. This difference is known as resonance energy
or delocalization energy. All resonance structures are not equivalent. The following rules help
determine whether or not a resonance structure will contribute significantly to the hybrid structure.

Rules of Resonance

Rule 1: The most significant resonance contributor has the greatest number of full octets (or if
applicable, expanded octets).

Rule 2: The most significant resonance contributor has the fewest atoms with formal charges.

3
Rule 3: If formal charges cannot be avoided, the most significant resonance contributor has the
negative formal charges on

the most electronegative atoms, and the positive formal charges on the least electronegative atoms.

Rule 4: The most significant resonance contributor has the greatest number of covalent bonds.

Rule 5: If a pi bond is present, the most significant resonance contributor has this pi bond between
atoms of the same row of the periodic table (usually carbon pi bonded to boron, carbon, nitrogen,
oxygen, or fluorine).

Rule 6: Aromatic resonance contributors are more significant than resonance contributors that are
not aromatic.

Mesomeric Effect

The permanent polarization of a group conjugated with a bond or a set of alternate bonds is
transmitted through the electrons of the system, resulting in a different distribution of electrons in
the unsaturated chain. This kind of electron distribution in unsaturated compounds conjugated with
electron-releasing or withdrawing groups or atoms is called mesomeric effect. An example is given
below:

In the groups shown below, a polarity is induced in compounds due to transfer of electrons through
bonds. This effect is a consequence of resonance and is seen in compounds that contain a double
bond that is separated from another double bond or a lone pair of electrons by a single bond.

4
The mesomeric effect can be subdivided into two types: Positive mesomeric effect (+M effect)
and Negative mesomeric effect (-M effect).

+M effect

When the electrons or the pi electrons are transferred from a particular group towards a conjugate
system, thus increasing the electron density of the conjugated system then such a phenomenon is
known as (+M) effect or positive mesomeric effect. Examples are shown below:

5
For the +M effect, the group should have either a lone pair of electrons or should have a negative
charge.The +M effect gives negative charge to the conjugate system or it can be said that the
electron density increases on the conjugate system due to this. These conjugate systems show more
reactivity towards electrophiles and less reactivity towards a nucleophile. Groups showing +M
effect include;

–NH, –NH2,–NHR, –NR2, – O, – OH, –OR, – F, – Cl, –O–COR, – NHCOR, –SH, – SR etc.

-M Effect

When the pi-bond electrons are transferred from the conjugate system to a particular group thus
the electron density of the conjugate system is decreased, then this phenomenon is known as
negative mesomeric (–M) effect.

For –M effect, the group should have either a positive charge or should have a vacant orbital. –
M effect makes the compound more reactive towards a nucleophile as it decreases the electron
density in the conjugate system and at the same time it is less reactive towards electrophile due to

6
same reasons. The group which shows –M effect include; –NO2, –CN, –COX, –SO3H, – CHO, –
CONH2, –COR, –COOH, –COOR etc.

Conclusively, mesomeric effect describes the distribution of the charge in the compound, helps to
decide the point at which electrophiles or nucleophiles attack. It is also useful in describing
physical characteristics such as dipole moment, bond length.

Hyper-conjugation

Hyper-conjugation helps explain the stability of alkyl radicals. It involves the delocalization of -
electrons belonging to the C-H bond of the alkyl group attached to an atom with an unshared
orbital. The more the hyper-conjugative hydrogen, the more is the stability. Hyper-conjugation is
the stabilizing interaction that results from the interaction of the electrons in a σ-bond (usually C-
H or C-C) with an adjacent empty or partially filled p-orbital or a π-orbital to give an extended
molecular orbital that increases the stability of the system. In contrast to resonance which involves
pi-bonds, hyper-conjugation involves a sigma bonds component, usually a C-C or C-H bond.
Hyper-conjugation explains why increasing the number of alkyl substituents on a carbocation or
radical centre leads to an increase in stability.

Considering how a methyl group (-CH3) is involved in hyper-conjugation with a carbocation

centre, it is important to draw it to show the C-H σ-bonds. Note that the empty p orbital associated
with the positive charge at the carbocation centre is in the same plane (i.e. coplanar) with one of
the C-H σ-bonds (shown in blue.) This geometry means the electrons in the σ-bond can be
stabilised by an interaction with the empty p-orbital of the carbocation centre (this diagram shows
the similarity with resonance and the structure on the right has the "double bond - no bond"
character)

7
8