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Volume 170, 2014
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The mechanochemical production of phenyl cations through heterolytic bond scission

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Abstract

High mechanical forces applied to polymeric materials typically induce unselective chain scission. For the last decade, mechanoresponsive molecules, mechanophores, have been designed to harness the mechanical energy applied to polymers and provide a productive chemical response. The selective homolysis of chemical bonds was achieved by incorporating peroxide and azo mechanophores into polymer backbones. However, selective heterolysis in polymer mechanochemistry is still mostly unachieved. We hypothesized that highly polarized bonds in ionic species are likely to undergo heterolytic bond scission. To test this, we examined a triarylsulfonium salt (TAS) as a mechanophore. Poly(methyl acrylate) possessing TAS at the center of the chain (PMA-TAS) is synthesized by a single electron transfer living radical polymerization (SET-LRP) method. Computational and experimental studies in solution reveal the mechanochemical production of phenyl cations from PMA-TAS. Interestingly, the generated phenyl cation reacts with its counter-anion (trifluoromethanesulfonate) to produce a terminal trifluoromethyl benzene structure that, to the best of our knowledge, is not observed in the photolysis of TAS. Moreover, the phenyl cation can be trapped by the addition of a nucleophile. These findings emphasize the interesting reaction pathways that become available by mechanical activation.

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Supplementary files

Article information


Submitted
28 Feb 2014
Accepted
26 Mar 2014
First published
26 Mar 2014

Faraday Discuss., 2014,170, 385-394
Article type
Paper
Author version available

The mechanochemical production of phenyl cations through heterolytic bond scission

T. Shiraki, C. E. Diesendruck and J. S. Moore, Faraday Discuss., 2014, 170, 385
DOI: 10.1039/C4FD00027G

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