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.