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Updated: May 28, 2025
From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
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.
Abstract:
The role of halogen bonding (HaB) in the reactions of N-chlorosuccinimide (SimCl), a versatile reagent in organic synthesis, was investigated through experimental and computational analyses of its interactions with halides. The reactions of SimCl with Br- or I- resulted in the crystallization of HaB complexes of chloride with N-iodosuccinimide (SimI) or N-bromosuccinimide (SimBr). Computational analysis revealed that halogen rearrangements, which occurred even at -73 °C, were facilitated by halogen bonding. The dissociation of SimCl∙Y- (Y = I or Br) complexes into a Sim- + ClY pair (followed by the rotation and re-binding of the interhalogen molecules) bypassed the formation of the high-energy Sim- + Cl+ pair and drastically (about tenfold) reduced the dissociation energy of the N-Cl bond. Furthermore, while the dissociation energy of individual SimCl is higher (and its HaB is weaker) compared to that of SimI or SimBr, the dissociation of the N-Cl bond in SimCl∙Y- requires less energy than in the complexes of SimBr or SimI. The facile cleavage of such bonds in HaB complexes explains the high reactivity of SimCl and its effectiveness as a halogenating agent.
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