Issue 28, 2024

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

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.

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

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Article information

Article type
Edge Article
Submitted
10 Apr 2024
Accepted
15 Jun 2024
First published
17 Jun 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 10803-10809

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

S. J. Kohl, L. M. Sigmund, M. Schmitt and L. Greb, Chem. Sci., 2024, 15, 10803 DOI: 10.1039/D4SC02378A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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