Electron Migration Effects - Organic Chemistry Notes
Electron Migration Effects
In organic molecules, the movement of electrons influences reactivity and stability. There are
several types of
electron migration effects, which are key to understanding organic reaction mechanisms.
1. Inductive Effect (I Effect)
Definition: It refers to the polarization of a sigma-bond due to the electronegativity difference
between atoms.
Key Concept: When a more electronegative atom pulls electrons towards itself, it creates a partial
negative charge on itself
and a partial positive charge on the adjacent atom.
Types:
-I Effect: Electron-withdrawing groups (like -NO2, -Cl) pull electrons away from the chain.
+I Effect: Electron-donating groups (like -CH3, -C2H5) push electrons towards the chain.
Impact on Stability:
- Electron-withdrawing groups stabilize negative charges.
- Electron-donating groups stabilize positive charges.
2. Resonance Effect (R Effect)
Definition: The delocalization of pi-electrons across conjugated systems in a molecule.
Key Concept: Electrons in pi-bonds or lone pairs can move across adjacent atoms, creating multiple
resonance structures.
Types:
+R Effect (Electron Donating via Resonance): Groups like -OH, -OR, and -NH2 donate electrons
through resonance, stabilizing carbocations.
-R Effect (Electron Withdrawing via Resonance): Groups like -NO2, -CN withdraw electrons via
resonance, stabilizing carbanions.
Impact on Reactivity:
- Resonance stabilizes intermediates in reactions, making the molecule more reactive in
electrophilic or nucleophilic attacks.
3. Hyperconjugation
Definition: The delocalization of electrons from a sigma-bond (usually C-H) into an adjacent empty
p-orbital or pi-system.
Key Concept: This interaction leads to the stabilization of carbocations, alkenes, and radicals.
Example: In propene (CH3-CH=CH2), the electrons from the C-H bond of the methyl group interact
with the pi-system of the double bond, stabilizing the molecule.
Impact on Stability:
- Hyperconjugation explains the stability order of carbocations: 3° > 2° > 1° > methyl.
- The greater the number of alkyl groups attached to a double bond or carbocation, the greater the
stabilization through hyperconjugation.
4. Electromeric Effect (E Effect)
Definition: It refers to the temporary shifting of electrons in a pi-bond in response to the approach of
an electrophile or nucleophile.
Key Concept: When an attacking reagent (like an electrophile) approaches a molecule, the
pi-electrons shift toward or away from the atom being attacked.
Types:
+E Effect (Electron Donating): The electrons in a pi-bond move towards the attacking electrophile.
-E Effect (Electron Withdrawing): The electrons in a pi-bond move away from the attacking
nucleophile.
Impact on Reactivity: This effect is temporary and happens only in the presence of a reagent,
enhancing the reactivity of double or triple bonds.
5. Mesomeric Effect (M Effect)
Often used interchangeably with the Resonance Effect, the mesomeric effect refers specifically to
the electron-withdrawing (-M)
or electron-donating (+M) effects of substituents in resonance structures.
Summary of Stability Influence:
- Electron-Donating Groups (+I, +R, +E): Stabilize positive charges (carbocations) and increase
electron density.
- Electron-Withdrawing Groups (-I, -R, -E): Stabilize negative charges (carbanions) and decrease
electron density.
