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🥼organic chemistry review

Heterolytic Cleavage

Written by the Fiveable Content Team • Last updated September 2025
Written by the Fiveable Content Team • Last updated September 2025

Definition

Heterolytic cleavage is a type of bond breaking process where a covalent bond is cleaved in an unsymmetrical manner, resulting in the formation of two charged species - a positively charged species (carbocation) and a negatively charged species (anion). This process is in contrast to homolytic cleavage, where the bond is broken equally to produce two neutral radical species.

5 Must Know Facts For Your Next Test

  1. Heterolytic cleavage is a key step in the E1 (Elimination, unimolecular) and E1cB (Elimination, conjugate base) reactions, where it leads to the formation of a carbocation intermediate.
  2. In the context of phenols and their uses, heterolytic cleavage can occur during the conversion of phenols to phenoxide ions, which are important intermediates in many reactions involving phenols.
  3. The formation of carbocations during heterolytic cleavage makes them susceptible to nucleophilic attack, leading to various substitution and addition reactions.
  4. The stability of the carbocation intermediate formed during heterolytic cleavage is a crucial factor in determining the feasibility and rate of the reaction.
  5. The nature of the leaving group and the reaction conditions (e.g., solvent, temperature) can influence the likelihood of heterolytic versus homolytic cleavage in organic reactions.

Review Questions

  • Explain the role of heterolytic cleavage in the E1 and E1cB reactions.
    • In the E1 and E1cB reactions, heterolytic cleavage is a key step that leads to the formation of a carbocation intermediate. In the E1 reaction, the leaving group departs first, creating a carbocation that is then eliminated by the removal of a proton. In the E1cB reaction, the base first removes a proton, generating a carbanion intermediate that then undergoes heterolytic cleavage to form the carbocation, which is subsequently eliminated. The stability of the carbocation intermediate is a crucial factor in determining the feasibility and rate of these elimination reactions.
  • Describe how heterolytic cleavage is involved in the conversion of phenols to phenoxide ions.
    • The conversion of phenols to phenoxide ions involves heterolytic cleavage. Phenols can undergo deprotonation, where the hydroxyl proton is removed by a base, resulting in the formation of a phenoxide ion. This process involves the heterolytic cleavage of the O-H bond, leading to the creation of a negatively charged phenoxide ion and a positively charged proton. The phenoxide ion is an important intermediate in many reactions involving phenols, as it can participate in further substitution, addition, or elimination reactions.
  • Analyze the factors that influence the likelihood of heterolytic versus homolytic cleavage in organic reactions.
    • The likelihood of heterolytic versus homolytic cleavage in organic reactions depends on several factors. The nature of the leaving group is crucial, as good leaving groups (e.g., halides, sulfonate esters) are more likely to undergo heterolytic cleavage, leading to the formation of carbocations. The reaction conditions, such as solvent polarity and temperature, also play a role. Polar solvents and higher temperatures tend to favor heterolytic cleavage, as they stabilize the charged intermediates. Additionally, the stability of the resulting carbocation is a significant factor, as more stable carbocations are more likely to form during heterolytic cleavage. Overall, the balance of these factors determines whether a reaction will proceed through a heterolytic or homolytic cleavage pathway.