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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
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Halogen Bonding and Rearrangements in Complexes of N-Chlorosuccinimide with Halides
Maison Hardin1, Matthias Zeller2, Sergiy V Rosokha1
1Department of Chemistry, Ball State University, Muncie, IN 47306, USA.
Molecules (Basel, Switzerland)
|February 13, 2025
Summary
Halogen bonding (HaB) significantly enhances the reactivity of N-chlorosuccinimide (SimCl) in organic synthesis. HaB complexes lower the energy barrier for N-Cl bond cleavage, making SimCl an effective halogenating agent.
Area of Science:
- Organic Chemistry
- Supramolecular Chemistry
- Computational Chemistry
Background:
- N-chlorosuccinimide (SimCl) is a widely used reagent in organic synthesis.
- Halogen bonding (HaB) is an important non-covalent interaction influencing chemical reactions.
- Understanding HaB's role in SimCl reactions is crucial for optimizing synthetic strategies.
Purpose of the Study:
- To investigate the role of halogen bonding in the reactivity of N-chlorosuccinimide (SimCl).
- To analyze the interactions between SimCl and halide ions (Br-, I-).
- To elucidate the mechanism by which HaB influences N-Cl bond dissociation.
Main Methods:
- Experimental crystallographic analysis of SimCl-halide complexes.
- Computational chemistry methods (e.g., DFT) to study interaction energies and reaction pathways.
- Thermodynamic analysis of N-Cl bond dissociation energies in various complexes.
Main Results:
- Formation of halogen bonding complexes between SimCl and iodide (I-) or bromide (Br-).
- Observation of halogen rearrangements facilitated by HaB, even at low temperatures (-73 °C).
- Significant reduction (approx. tenfold) in the N-Cl bond dissociation energy within HaB complexes.
- Lower energy requirement for N-Cl bond cleavage in SimCl complexes compared to SimBr or SimI complexes.
Conclusions:
- Halogen bonding plays a critical role in activating SimCl for reactions.
- HaB complexes provide a lower energy pathway for N-Cl bond cleavage, bypassing high-energy intermediates.
- The enhanced reactivity of SimCl as a halogenating agent is attributed to its ability to form stabilizing HaB complexes.
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