Issue 10, 2023

Mechanochemical solid state single electron transfer from reduced organic hydrocarbon for catalytic aryl-halide bond activation

Abstract

Solid-state radical generation is an attractive but underutilized methodology in the catalytic strong bond activation process, such as the aryl-halide bond. Traditionally, such a process of strong bond activation relied upon the use of transition metal complexes or strongly reducing photocatalysts in organic solvents. The generation of the aryl radical from aryl halides in the absence of transition-metal or external stimuli, such as light or cathodic current, remains an elusive process. In this study, we describe a reduced organic hydrocarbon, which can act as a super reductant in the solid state to activate strong bonds by solid-state single electron transfer (SSSET) under the influence of mechanical energy leading to a catalytic strategy based on the mechano-SSSET or mechanoredox process. Here, we investigate the solid-state synthesis of the super electron donor phenalenyl anion in a ball mill and its application as an active catalyst in strong bond (aryl halide) activation. Aryl radicals generated from aryl halides by employing this strategy are competent for various carbon–carbon bond-forming reactions under solvent-free and transition metal-free conditions. We illustrate this approach for partially soluble or insoluble polyaromatic arenes in accomplishing solid–solid C–C cross-coupling catalysis, which is otherwise difficult to achieve by traditional methods using solvents.

Graphical abstract: Mechanochemical solid state single electron transfer from reduced organic hydrocarbon for catalytic aryl-halide bond activation

Supplementary files

Article information

Article type
Edge Article
Submitted
06 nov 2022
Accepted
02 feb 2023
First published
02 feb 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 2606-2615

Mechanochemical solid state single electron transfer from reduced organic hydrocarbon for catalytic aryl-halide bond activation

A. Biswas, A. Bhunia and S. K. Mandal, Chem. Sci., 2023, 14, 2606 DOI: 10.1039/D2SC06119H

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