Mandal, Debdeep;
Demirer, T Ilgin;
Sergeieva, Tetiana;
Morgenstern, Bernd;
Wiedemann, Haakon TA;
Kay, Christopher WM;
Andrada, Diego M;
(2023)
Evidence of AlII Radical Addition to Benzene.
Angewandte Chemie
, 135
(13)
, Article e202217184. 10.1002/ange.202217184.
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Abstract
Electrophilic AlIII species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low-valent AlI aluminyl anions have showcased oxidative additions towards arenes C−C and/or C−H bonds. Herein, we communicate compelling evidence of an AlII radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC8 in benzene furnishes a double addition to the benzene ring instead of a C−H bond activation, producing the corresponding cyclohexa-1,3(orl,4)-dienes as Birch-type reduction product. X-ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable AlII radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection.
| Type: | Article |
|---|---|
| Title: | Evidence of AlII Radical Addition to Benzene |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1002/ange.202217184 |
| Publisher version: | https://doi.org/10.1002/ange.202217184 |
| Language: | English |
| Additional information: | © 2023 The Authors. Angewandte Chemie published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > London Centre for Nanotechnology |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10168554 |
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