Redox activation of halogen-bonding catalysts for organic synthesis
Abstract
Among non-covalent interactions, halogen bonding (XB) has emerged as a sophisticated tool for molecular assembly and catalysis, distinguished from its hydrogen bonding (HB) analogues by its superior directionality and the high polarizability of the halogen atom. These characteristics offer unique opportunities for fine-tuning the strength and the geometry of this interaction to achieve targeted functionalities. Furthermore, the use of a redox-active moiety enables a controlled increase in the XB donor strength upon oxidation, effectively activating the XB donor catalyst. Herein, we report the rational design and the synthesis of ferrocene-based XB donors. Characterization of the fundamental XB interactions in the system was performed through a synergistic approach involving single-crystal X-ray diffraction and solution-phase binding studies. Density Functional Theory (DFT) analysis reveals a significant amplification of the ‘σ-hole’ intensity upon oxidation, a feature we exploit to drive catalytic turnover. Notably, these redox-switchable iodoferrocene derivatives serve as potent catalysts for XB-mediated Friedel–Crafts alkylation reactions, even in competitive polar solvents—a challenging environment for traditional XB catalysis. This work demonstrates the efficacy of charge modulation by redox activation in fine-tuning XB strength for organic transformation.
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BibTeX
@article{groni2026redox,
title = {{Redox activation of halogen-bonding catalysts for organic synthesis}},
author = {Sihem Groni and Sercan Akbaba and Uchral Otgonbayar and Jérémy Forté and Stefan Huber and Sitthichok Kasemthaveechok and Bernd Schöllhorn and Claire Fave},
journal = {Chemical Science},
year = {2026},
month = sep,
doi = {10.1039/d6sc02883g},
url = {https://hal.science/hal-05665603v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - Redox activation of halogen-bonding catalysts for organic synthesis
AU - Sihem Groni
AU - Sercan Akbaba
AU - Uchral Otgonbayar
AU - Jérémy Forté
AU - Stefan Huber
AU - Sitthichok Kasemthaveechok
AU - Bernd Schöllhorn
AU - Claire Fave
PY - 2026
DA - 2026/09/08
JO - Chemical Science
DO - 10.1039/d6sc02883g
UR - https://hal.science/hal-05665603v1
AB - Among non-covalent interactions, halogen bonding (XB) has emerged as a sophisticated tool for molecular assembly and catalysis, distinguished from its hydrogen bonding (HB) analogues by its superior directionality and the high polarizability of the halogen atom. These characteristics offer unique opportunities for fine-tuning the strength and the geometry of this interaction to achieve targeted functionalities. Furthermore, the use of a redox-active moiety enables a controlled increase in the XB donor strength upon oxidation, effectively activating the XB donor catalyst. Herein, we report the rational design and the synthesis of ferrocene-based XB donors. Characterization of the fundamental XB interactions in the system was performed through a synergistic approach involving single-crystal X-ray diffraction and solution-phase binding studies. Density Functional Theory (DFT) analysis reveals a significant amplification of the ‘σ-hole’ intensity upon oxidation, a feature we exploit to drive catalytic turnover. Notably, these redox-switchable iodoferrocene derivatives serve as potent catalysts for XB-mediated Friedel–Crafts alkylation reactions, even in competitive polar solvents—a challenging environment for traditional XB catalysis. This work demonstrates the efficacy of charge modulation by redox activation in fine-tuning XB strength for organic transformation.
SN - 2041-6520
SN - 2041-6539
ER -