Metal-ligand cooperativity of the calix(4)pyrrolato aluminate

• Verfasst von: Ebner, Fabian [VerfasserIn]
• Verfasst von: Sigmund, Lukas M. [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Metal-ligand cooperativity of the calix(4)pyrrolato aluminate
• Titelzusatz: triggerable C-C bond formation and rate control in catalysis
• Verf.angabe: Fabian Ebner, Lukas Maximilian Sigmund, and Lutz Greb
• E-Jahr: 2020
• Jahr: 23 June 2020
• Umfang: 7 S.
• Fussnoten: Im Titel steht die 4 in eckiger Klammer ; Gesehen am 02.11.2021
• Titel Quelle: Enthalten in: Angewandte Chemie. International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2020
• Band/Heft Quelle: 59(2020), 39, Seite 17118-17124
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202007717
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: aluminum
• Sach-SW: calix4pyrrole
• Sach-SW: dynamic covalent chemistry
• Sach-SW: metal-ligand cooperativity
• Sach-SW: structural constraint
• K10plus-PPN: 1775850439
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Metal-ligand cooperativity (MLC) had a remarkable impact on transition metal chemistry and catalysis. By use of the calix[4]pyrrolato aluminate, [1]−, which features a square-planar AlIII, we transfer this concept into the p-block and fully elucidate its mechanisms by experiment and theory. Complementary to transition metal-based MLC (aromatization upon substrate binding), substrate binding in [1]− occurs by dearomatization of the ligand. The aluminate trapps carbonyls by the formation of C−C and Al−O bonds, but the products maintain full reversibility and outstanding dynamic exchange rates. Remarkably, the C−C bonds can be formed or cleaved by the addition or removal of lithium cations, permitting unprecedented control over the system's constitutional state. Moreover, the metal-ligand cooperative substrate interaction allows to twist the kinetics of catalytic hydroboration reactions in a unique sense. Ultimately, this work describes the evolution of an anti-van't Hoff/Le Bel species from their being as a structural curiosity to their application as a reagent and catalyst.