Cover Image

Nitrogen monoxide and calix[4]pyrrolato aluminate: structural constraint enabled NO dimerization

Show other versions (1)

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 constra...

Full description

Saved in:
Bibliographic Details
Main Authors: Kohl, Senta J. (Author) , Sigmund, Lukas M. (Author) , Schmitt, Manuel (Author) , Greb, Lutz (Author)
Format: Article (Journal)
Language:English
Published: 17 Jun 2024
In: Chemical science
Year: 2024, Volume: 15, Issue: 28, Pages: 10803-10809
ISSN:2041-6539
DOI:10.1039/D4SC02378A
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1039/D4SC02378A
Verlag, kostenfrei, Volltext: https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc02378a
Get full text
Author Notes:Senta J. Kohl, Lukas M. Sigmund, Manuel Schmitt and Lutz Greb
Description
Summary: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.
Item Description:Zuerst veröffentlicht: 17. Juni 2024
Gesehen am 14.11.2024
Physical Description:Online Resource
ISSN:2041-6539
DOI:10.1039/D4SC02378A

Similar Items