Donor-free 9,10-dihydro-9,10-dialuminaanthracenes.

Autor: Lückert PL; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt Max-von-Laue-Straße 7 D-60438 Frankfurt (Main) Germany matthias.wagner@chemie.uni-frankfurt.de., Gilmer J; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt Max-von-Laue-Straße 7 D-60438 Frankfurt (Main) Germany matthias.wagner@chemie.uni-frankfurt.de., Virovets A; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt Max-von-Laue-Straße 7 D-60438 Frankfurt (Main) Germany matthias.wagner@chemie.uni-frankfurt.de., Lerner HW; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt Max-von-Laue-Straße 7 D-60438 Frankfurt (Main) Germany matthias.wagner@chemie.uni-frankfurt.de., Wagner M; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt Max-von-Laue-Straße 7 D-60438 Frankfurt (Main) Germany matthias.wagner@chemie.uni-frankfurt.de.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2024 Nov 18; Vol. 16 (1), pp. 147-155. Date of Electronic Publication: 2024 Nov 18 (Print Publication: 2024).
DOI: 10.1039/d4sc06940d
Abstrakt: Despite their promising potential, e.g. , as ditopic, cooperatively binding Lewis acids, 9,10-dihydro-9,10-dialuminaanthracenes (DAA-R 2 ; R: terminal Al-bonded substituent) have remained unexplored for long due to the challenges in synthesizing the ligand-free species. We demonstrate that DAA-Me 2 is accessible via the reaction of 1,2-(Me 3 Sn) 2 C 6 H 4 with AlMe 3 , producing volatile SnMe 4 as the sole byproduct. In non-coordinating solvents and in the solid state, DAA-Me 2 exists as a dimer (DAA-Me 2 ) 2 . Treatment of (DAA-Me 2 ) 2 with 4 equiv. AlBr 3 cleaves the dimer, leads to quantitative Me/Br exchange, and forms the double AlBr 3 adduct DAA-Br 2 ·(AlBr 3 ) 2 . Removal of AlBr 3 with 2,2'-bipyridine gives free DAA-Br 2 , which also dimerizes in the absence of bases to form (DAA-Br 2 ) 2 . (DAA-Me 2 ) 2 and (DAA-Br 2 ) 2 readily react with mono- ( e.g. , pyridine) or ditopic Lewis bases ( e.g. , potassium pyrazolide) to afford trans -diadducts or triptycene-type frameworks. Upon addition of [ n Bu 4 N]Br, DAA-Br 2 ·(AlBr 3 ) 2 undergoes selective cleavage of Al-C bonds to produce the Br - chelate complex of 1,2-(Br 2 Al) 2 C 6 H 4 , a valuable synthon for 1,2-dideprotonated benzenes.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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