Lecture on Reaction Mechanism

Presented by:-
Dr. Santosh Singh
Assistant Professor
D.D.U. Govt. P.G. College, Saidabad,
Prayagraj
 Reaction mechanism

Electronic displacement
Electronic displacementin Electronic
Fission displacement
of bonds Naturedisplacement
Electronic of attacking
covalent
in bond
covalent bond in covalent bond in covalentreagent
bond

Inductive effect
Mesomeric effect or Homolytic Heterolytic Electrophile Nucleophile
resonance effect
Electronic effect All positively charged species having vacant
Hyperconjugation p-orbital
Anomeric effect All neutral molecule having incomplete octet
All neutral molecule having vacant d-orbital

Electronic displacement in covalent bond:- For any reaction, the electronic displacement must occurs in the
covalent bond of substrate. These are following effects which are responsible for electronic displacement of covalent bond.
 Inductive effect
 Mesomeric effect or Resonance
 Electromeric effect
 Hyperconjugation
 Anomeric effect
Due to electronic displacement in covalent bond, same electron deficient and same electron
rich centre arises in the molecule thus the molecule become polar and reactive

eg: i) (Inductive Effect)

 electron displacement toward more electronegative atom

ii)
( Mesomeric effect)
 electron displace due to
conjugation Electron deficient Electron rich

iii)
Displacement of  electron due to presence of attacking reagent

iv)
(Hyperconjugation)
Displacement of  electron with  electron

v)
(Anomeric Effect)
 Inductive Effect
Inductive Effect : Polarity produce in a molecule due to displacement of  electron toward the more
electronegative atom is known as Inductive Effect . For eg.

 electron displacement toward

I -Effect more electronegative atom

I -Effect I -Effect

Displacement of  electron away from a group
or atom are called +I –Effect. For eg :
All alkyl group behaves as +I group.
Exception case organo-metallic compound alkyl
group behaves as - I –Effect . For eg : -R-Mg-X
Displacement of sigma electrons towards a group
or atom are called - I –Effect.
All positively charged group behaves as -I
group For eg :
 All electronegative atoms behave as -I group.
For e.g:
F, Cl, Br, I, –NO2, –CN,-SH, SR, -+CH2 etc

Electronegative atoms having negative charge & with

complete octet also behaves as +I group for eg: O- , COO-
 Salient features of inductive effects
Only sigma electrons are involved.
 It is a permanent effect.
 Inductive effect depends on distance from source atom.
 It affect physical and chemical property of the molecule.

Application of Inductive effect

Acidic strength:-

P Conjugate base of acid (P)

Acidic strength  Stability of conjugate base

Case I- When G is +I group

Increasing the magnitude of negative charge stability decreases

Acidic strength also decreases
Case II- When G is -I group

Increasing the stability by decreasing the magnitude of

-I Effect negative charge
 Acidic strength increases due to increase of –I effect

Basic strength of amine :

When G is +I group

Basicity  +I effect

Basicity increases on increasing +I effect

 Conjugation

Conjugation arises in a molecule due to interaction between two molecular orbital in which one
molecular orbital is filled whereas other molecular orbital is vacant.

For conjugation, each atom must be present on sp2 hybridization and shape should be planar.
 Types of conjugation
1- b - *

b *

b *

b *
2- n- *

* n

Note:-
In conjugation or mesomeric effect only - electrons & lone pair electron present in p- orbital participate.
 Hybrid orbital does not participate in conjugation.
For conjugation molecular orbital or atomic orbital must be present in same plane.
3. b- vacant p orbital interaction:-

4. b- p orbital having single e-interaction :

 Mesomeric effect

Polarity produced in a molecule due to displacement of π-electrons in a conjugated molecules. For eg.

 Conjugation is necessary condition for mesomeric effect.

 In this effect, only π- electrons and lone pair of electrons participate.

 It is a permanent effect and does not depends on distance.

 It also affect physical and chemical properties of the molecules.

 M effect

-M effect
+M effect
Displacement of π electrons away from a Displacement of π electrons towards a
group or atom in conjugated molecules is group or atom in conjugated molecules is
known as +M- effect. known as –M - effect.
+M group are those group which contain at -M effect group are those group which
least one high energy filled orbital contain low energy vacant d or π* orbital.
(lone pair)

e.g.
-OH , -NH2 ,-OCH3, -SH , -SCH3 , -F , -Cl , -
Br , -I etc.
 All +M group are ortho & para directing group All –M group behaves as meta directing group

 All +M group also shows –I effect All +M group also shows –I effect.

 +M effect is directly proportional to the energy of For eg:

lone pair

 +M effect order:- NH2 › OH › I › Br › Cl › F

-M effect order:

Energy of * increases, -I effect decreases

+M effect is not exerted due to

+M effect is exerted C=O improper orientation but
break easily -Ieffect is exerted by C-O bond
hence C=O frequency increases
 Electromeric effect
Polarity produce in a molecule due to displacement of π electronson the demand of attacking reagent is
known as Electronic effect.
 Hyperconjugation

The interaction of sigma bonding molecular orbital with either vacant * or vacant p orbital or vacant
* orbital or with vacant d orbital or p orbital having single electron are known as hyperconjugation.
For eg:

b * b p b
b p *

b - * b - p b - p b - *

Effective hyperconjugation order :

b – p  b - *  b - *  b - *
 Application of Hyperconjugation

Stability of alkene :
Stability of alkene  No of hyperconjugative structure

Stability order of alkene : i) > ii) >iii

Active hydrogen containing Compounds :

Energy of * ( C=O) increases due to either +I effect and +M effect

Hyperconjugation decreases, acidity decreases

 Acidic strength of nitro alkane is more than aldehyde due to hyperconjugation

Stability of Carbocation:

Stability of carbocation  No of hyperconjugative structure

Stability order of carocation

i) > ii)> iii)
Lewis acidic character of Boran compounds :

Lewis acidic character of Flouro compounds :

Acidity Order of flouro compounds :

acidity increases due to increase of hyperconjugation

 Anomeric effect
The interaction between non-bonding molecular orbital with vacant σ* molecular orbital is
known as anomeric effect. Anomeric effect generally arises in cyclic molecule.

The interaction b/w non-bonding M.O. with vacant s* M.O. is known as anomeric effect

Non-bonding & * must be antiperiplanar

*

n * Anomeric effect dominate over 1,3- interaction

*

* * Anti form more stable due to anomeric effect

* Anomeric effect also known as reverse hyper-
* conjugation
 Resonance effect

Resonance effect: -
If there are several structures require for explanation of a molecule or to define the property of the molecule
then we say that the molecule shows resonance & these structures are called resonating structure. Resonance
either arises due to localisation of π-electrons or σ electrons. All mesomeric effect, hyperconjugation,
anomeric effect is also resonance effect.

Characteristics of Resonating structure: -

 The relative positions of atom in all resonating structure does not change i.e. only displacement of σ or π-
electrons take place during resonance.
 The number of paired (bond pair + lone pair) & unpaired electrons in each reaction structure are same.
 The energy of all resonating structure is nearly same (for mesomeric effect).

If a molecule shows resonance then resonance hybrid is the structure which completely define the molecule.
In Resonance hybrid, all resonating structures contribute. The extent of contribution is directly proportional
to stability of resonating structure.
 Stability of Resonating structure

 Neutral resonating structure are more stable than charged resonating structure
Or
Resonating structure having more covalent bond are more stable
Or
Resonating structure in which each atom present with complete octet is more stable
For eg.

A is more stable than B and C because A is neutral, contains more covalent bond and have
complete octet.
 In case of charged resonating structure, resonance structure having minimum opposite charge
separation and maximum same charge separation is more stable.
B is more stable than C
 Resonating structure in which negative charge present on electronegative atom and positively
charge present on electropositive atom are more stable. For eg.

S is more stable than R because negative charge present on electronegative atom.

 Bond order of some Molecule
Diatomic molecules

O2 O 2- O 2+ O22-

2.0 1.5 2.5 1

𝑩𝒐𝒏𝒅 𝒔𝒕𝒓𝒆𝒏𝒈𝒕𝒉
𝑩𝒐𝒏𝒅 𝒐𝒓𝒅𝒆𝒓 𝜶
𝑩𝒐𝒏𝒅 𝒍𝒆𝒏𝒈𝒕𝒉

Polyatomic molecule: -

Bond order of CO32- is 1.33

Bond order of benzene is 1.5