Environmental Sciences and Green Chemistry

Netaji Subhas University of Technology (NSUT)

Department of Chemistry

Notes
by
Dr. Nancy Gupta
 Electronic effects/ displacement
influences the structure, reactivity, or properties of molecule under the influence of an atom or
a substituent group or in the presence of an appropriate attacking reagent

These effects are dependent on the valence, bonding order and electronegativity of atoms,
polarity of a group as well as the molecular geometry

Types of electronic displacement

Permanent: under the influence of an atom or a substituent group

• The Inductive Effect

• Resonance / Mesomeric Effect
• Hyperconjugation

Temporary: in the presence of an attacking reagent

• Electromeric Effect
Applications
 Inductive effect
local change in the electron density due to electron-withdrawing or electron-donating
groups elsewhere in the molecule, resulting in a permanent dipole in a bond.

• covalent σ-bond not through pi bond

• dissimilar electronegativity
• Permanent partial displacement of electrons
• partial negative charge (δ–) more electronegative atom
• partial positive charge (δ+) on the other
• Polarization of covalent bond
• symbol (–>–) arrow towards more electronegative atom

+I Effect -I Effect
• more the number of resonance structure more is the stability of the molecule
• None of them can explain all the properties of molecules
• All resonating structures can be mixed to form hybrid structure
Criteria to have resonance
Presence of π electrons and conjugated system
 Hyperconjugation
• No bond resonance
• Presence of α – hydrogen is required (on the carbon adjacent to double bond)
• Happens through the overlapping of p-orbitals of a double bond and σ orbital of adjacent
single bond
• No bond resonance
• H+ ions are not free to move, they are still bound to firmly to the π cloud
 Consequences/ effect of hyperconjugation effect

Shortening of C- C bond adjacent to a double bond

Relative stability of alkenes:
Stability of carbocations

Stability of free radicals

 Electromeric effect
• Polarisable pi (π) bond
• Complete transfer of electrons of a multiple bond
• In the presence of attacking reagent
• reversible reaction
• If the groups linked to a multiple bond are similar, shift can occur in either direction
• If dissimilar groups are linked on the ends of the double bond, shift of the electron pair is
decided by the inductive effect

+E
Transfer of electrons to the atom on
which it is attacking

-E

Transfer of electrons to the atom other

than the one on which it is attacking
HCOOH, CH3COOH, CH3CH2COOH (Increasing order of acidity)
CH2(NO2) COOH, CH2(CN)COOH (Which is more acidic)

C6H5NH2, C6H5NHCH3, C6H5N(CH3)2 (Increasing order of basicity)