Catalytic activation via π-backbonding in halogen bonds†
‡a
and
Pierre
Kennepohl
*ab
Abstract
The role of halogen bonding (XB) in chemical catalysis has largely involved using XB donors as Lewis acid activators to modulate the reactivity of partner Lewis bases. We explore a more uncommon scenario, where a Lewis base modulates reactivity via a spectator halogen bond interaction. Our computational studies reveal that spectator halogen bonds may play an important role in modulating the rate of SN2 reactions. Most notably, π acceptors such as PF3 significantly decrease the barrier to substitution by decreasing electron density in the very electron rich transition state. Such π-backbonding represents an example of a heretofore unexplored situation in halogen bonding: the combination of both σ-donation and π-backdonation in this “non-covalent” interaction. The broader implications of this observation are discussed.
- This article is part of the themed collection: Harnessing non-covalent interactions for synthesis and catalysis
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