Please use this identifier to cite or link to this item: doi:10.22028/D291-39480
Title: Evidence of AlII Radical Addition to Benzene
Author(s): Mandal, Debdeep
Demirer, T. Ilgin
Sergeieva, Tetiana
Morgenstern, Bernd
Wiedemann, Haakon T. A.
Kay, Christopher W. M.
Andrada, Diego M.
Language: English
Title: Angewandte Chemie
Volume: 62
Issue: 13
Publisher/Platform: Wiley
Year of Publication: 2023
Free key words: Aluminum
EPR Spectroscopy
Low-Valent Compounds
Radicals
Structure Elucidation
DDC notations: 500 Science
Publikation type: Journal Article
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.
DOI of the first publication: 10.1002/anie.202217184
URL of the first publication: https://onlinelibrary.wiley.com/doi/10.1002/anie.202217184
Link to this record: urn:nbn:de:bsz:291--ds-394808
hdl:20.500.11880/35601
http://dx.doi.org/10.22028/D291-39480
ISSN: 1521-3773
1433-7851
Date of registration: 6-Apr-2023
Description of the related object: Supporting Information
Related object: https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.202217184&file=anie202217184-sup-0001-4444_a_sq.cif
https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.202217184&file=anie202217184-sup-0001-misc_information.pdf
https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.202217184&file=anie202217184-sup-0001-sh4310_a.cif
https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.202217184&file=anie202217184-sup-0001-sh4347_a.cif
https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.202217184&file=anie202217184-sup-0001-sh4952_a.cif
Faculty: NT - Naturwissenschaftlich- Technische Fakultät
Department: NT - Chemie
Professorship: NT - Prof. Dr. Christopher Kay
NT - Prof. Dr. Guido Kickelbick
NT - Prof. Dr. David Scheschkewitz
Collections:SciDok - Der Wissenschaftsserver der Universität des Saarlandes

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