IB Chemistry R3.4 R3.4.11
R3.4.11 HL

Electrophilic Addition Mechanisms

Key Concept

At HL you must be able to draw the full mechanism (with curly arrows) for electrophilic addition reactions of alkenes. These are two-step mechanisms proceeding via a carbocation intermediate.

Mechanism: Ethene + HBr

Electrophilic Addition of HBr to Ethene Step 1 (slow): π bond attacks δ+ hydrogen H₂C CH₂ H-Br δ+ δ- CH₃ CH₂⁺ Carbocation + Br⁻ Step 2 (fast): Br⁻ nucleophile attacks carbocation CH₃CH₂⁺ Br⁻ CH₃CH₂Br Bromoethane The π bond electrons are donated to H⁺, forming a carbocation. Then Br⁻ donates a lone pair to the C⁺.

Step-by-Step Explanation

Step 1 (slow):

  1. The electron-rich π bond of the alkene acts as a nucleophile
  2. A curly arrow goes from the π bond to the δ+ H in HBr (new C-H bond forms)
  3. Simultaneously, the H-Br bond breaks heterolytically (curly arrow from bond to Br)
  4. Products: a carbocation intermediate + Br⁻

Step 2 (fast):

  1. Br⁻ acts as a nucleophile and donates a lone pair to the positive carbon
  2. A new C-Br bond forms → final product

Mechanism: Ethene + Br₂

Induced Dipole Mechanism

Step 1: As Br₂ approaches the C=C, the π electrons repel the Br-Br bonding electrons. This creates an induced dipole (the nearer Br becomes δ+, the further Br becomes δ-).

Step 2: The π bond attacks the δ+ Br. The Br-Br bond breaks heterolytically → carbocation + Br⁻.

Step 3: Br⁻ attacks the carbocation → 1,2-dibromoethane.

Curly Arrow Checklist

  • Arrow 1: from the C=C π bond to the δ+ atom of the electrophile
  • Arrow 2: from the breaking bond in the electrophile to the more electronegative atom
  • Arrow 3 (step 2): from the lone pair on the anion to the C⁺ of the carbocation
  • All arrows are double-headed (showing electron pairs, not single electrons)

Think About It

Why is the π bond the part of the alkene that reacts, not the σ bond?

The π bond electrons are held in a region above and below the plane of the molecule, making them more exposed and accessible. The σ bond electrons are localised directly between the two carbon nuclei and are harder to reach. The π bond is also weaker than the σ bond, so it breaks more easily.

Common Exam Mistakes

  • Forgetting to show the carbocation intermediate. This is a two-step mechanism, not concerted.
  • Drawing the first curly arrow starting from HBr. It must start from the π bond (the alkene is the nucleophile in step 1).
  • Not showing the induced dipole on Br₂. Without this, Br₂ has no electrophilic centre.
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