Nitrogen monoxide and calix[4]pyrrolato aluminate

• Verfasst von: Kohl, Senta J. [VerfasserIn]
• Verfasst von: Sigmund, Lukas M. [VerfasserIn]
• Verfasst von: Schmitt, Manuel [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Nitrogen monoxide and calix[4]pyrrolato aluminate
• Titelzusatz: structural constraint enabled NO dimerization
• Verf.angabe: Senta J. Kohl, Lukas M. Sigmund, Manuel Schmitt and Lutz Greb
• E-Jahr: 2024
• Jahr: 17 Jun 2024
• Umfang: 7 S.
• Illustrationen: Illustrationen
• Fussnoten: Zuerst veröffentlicht: 17. Juni 2024 ; Gesehen am 14.11.2024
• Titel Quelle: Enthalten in: Chemical science
• Ort Quelle: Cambridge : RSC, 2010
• Jahr Quelle: 2024
• Band/Heft Quelle: 15(2024), 28, Seite 10803-10809
• ISSN Quelle: 2041-6539
• DOI: doi:10.1039/D4SC02378A
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1908546603

Abstract

The dimerization of nitrogen monoxide (NO) is highly relevant in homo- and heterogeneous biochemical and environmental redox processes, but a broader understanding is challenged by the endergonic nature of this equilibrium. The present work describes NO-dimerization leveraged by structurally constrained aluminum and metal-ligand cooperativity at the anionic calix[4]pyrrolato aluminate(III). Quantum chemical calculations reveal the driving force for N-N bond formation, while reactivity tests shed light on subsequent redox chemistry and NO decomposition at metal surfaces. Inhibiting the dimerization pathway by saturating NO's unpaired electron with a phenyl group (nitrosobenzene) allows trapping the 1,2-adduct as a key intermediate. Elevated temperatures result in an unprecedented and high-yielding rearrangement of the calix[4]pyrrolato ligand scaffold. Kinetic and theoretical studies provide a comprehensive picture of the rearrangement mechanism and delineate systematics for ring modification of the prominent calix[4]pyrrole macrocycle.