Volume 244, 2023

Catalytic activation via π-backbonding in halogen bonds

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.

Graphical abstract: Catalytic activation via π-backbonding in halogen bonds

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
20 Okt 2022
Accepted
04 Jan 2023
First published
10 Jan 2023

Faraday Discuss., 2023,244, 241-251

Catalytic activation via π-backbonding in halogen bonds

A. Wang and P. Kennepohl, Faraday Discuss., 2023, 244, 241 DOI: 10.1039/D2FD00140C

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