Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound

The large steric profile of the N-heterocyclic boryloxy ligand, –OB­(NDippCH)2, and its ability to stabilize the metal-centered HOMO, are exploited in the synthesis of the first example of a “naked” acyclic aluminyl complex, [K­(2.2.2-crypt)]­[Al­{OB­(NDippCH)2}2]. This system, which is formed by su...

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Bibliografski detalji
Glavni autori: Sarkar, D, Vasko, P, Roper, AF, Crumpton, AE, Roy, MMD, Griffin, LP, Bogle, C, Aldridge, S
Format: Journal article
Jezik:English
Izdano: American Chemical Society 2024
Opis
Sažetak:The large steric profile of the N-heterocyclic boryloxy ligand, –OB­(NDippCH)2, and its ability to stabilize the metal-centered HOMO, are exploited in the synthesis of the first example of a “naked” acyclic aluminyl complex, [K­(2.2.2-crypt)]­[Al­{OB­(NDippCH)2}2]. This system, which is formed by substitution at AlI (rather than reduction of AlIII), represents the first O-ligated aluminyl compound and is shown to be capable of hitherto unprecedented reversible single-site [4 + 1] cycloaddition of benzene. This chemistry and the unusual regioselectivity of the related cycloaddition of anthracene are shown to be highly dependent on the availability (or otherwise) of the K+ countercation.