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

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...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2024-07, Vol.15 (28), p.183-189
Main Authors: Kohl, Senta J, Sigmund, Lukas M, Schmitt, Manuel, Greb, Lutz
Format: Article
Language:English
Subjects:
Chemical bonds
Chemistry
Decomposition reactions
Dimerization
High temperature
Ligands
Metal surfaces
Nitric oxide
Nitrogen
Quantum chemistry
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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. The dimerization of nitrogen monoxide (NO) is highly relevant in biochemical and environmental redox processes. Here, it is shown how structral constraint and element-ligand cooperativity can steer this reaction.
ISSN:2041-6520
2041-6539
DOI:10.1039/d4sc02378a