Calix[4]pyrrolato aluminates

• Verfasst von: Ebner, Fabian [VerfasserIn]
• Verfasst von: Mainik, Philipp [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Calix[4]pyrrolato aluminates
• Titelzusatz: the effect of Ligand Modification on the reactivity of square-planar aluminum anions
• Verf.angabe: Fabian Ebner, Philipp Mainik, Lutz Greb
• Jahr: 2021
• Umfang: 5 S.
• Fussnoten: Gesehen am 20.04.2023
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2021
• Band/Heft Quelle: 27(2021), 16, Seite 5120-5124
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.202005493
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: aluminum
• Sach-SW: anti-van ’t Hoff-Le Bel
• Sach-SW: calix4pyrrole
• Sach-SW: Lewis acid
• Sach-SW: planar aluminate
• K10plus-PPN: 1843298546
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Structural constraint represents an attractive tool to modify p-block element properties without the need for unusual oxidation or valence states. The recently reported methyl-calix[4]pyrrolato aluminate established the effect of forcing a tetrahedral aluminum anion into a square-planar coordination mode. However, the generality of this structural motif and any consequence of ligand modification remained open. Herein, a systematic ligand screening was launched, and the class of square-planar aluminum anions was extended by two derivatives that differ in the meso-substitution at the calix[4]pyrrolato ligand. Strikingly, this modification provoked opposing trends in the preference for a Lewis acidic binding mode with σ-donors versus the aluminum-ligand cooperative binding mode with carbonyls. Insights into the origin of these counterintuitive experimental observations were provided by computation and bond analysis. Importantly, this rationale might allow to exploit mode-selective binding for catalytic rate control.