Evidence of AlII Radical Addition to Benzene |
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| Authors: | Dr Debdeep Mandal T Ilgin Demirer Dr Tetiana Sergeieva Dr Bernd Morgenstern Haakon T A Wiedemann Prof Dr Christopher W M Kay Dr Diego M Andrada |
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| Institution: | 1. General and Inorganic Chemistry Department, University of Saarland, Campus C4.1, 66123 Saarbrücken, Germany;2. Physical Chemistry Department, University of Saarland, Campus B2.2, 66123 Saarbrücken, Germany |
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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. |
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| Keywords: | Aluminum EPR Spectroscopy Low-Valent Compounds Radicals Structure Elucidation |
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