Radical NO2: Unlocking Nitrogen and Oxygen Transfer via Nickel Catalysis

Descrizione del progetto

Trasferimento di azoto e ossigeno catalizzato dal nichel mediante NO₂

Il biossido di azoto (NO₂), un radicale persistente e un sottoprodotto della combustione, ha potenzialità enormi come reagente nella chimica sintetica grazie alla sua insolita reattività a un solo elettrone. Con il sostegno del programma di azioni Marie Skłodowska-Curie, il progetto NOVa si propone di definire nuove vie sintetiche, rivelare nuovi modi di reattività dei radicali persistenti e migliorare la comprensione degli intermedi organometallici. Per farlo, indagherà le trasformazioni catalizzate dal nichel in condizioni blande, sfruttando la reattività dell’NO₂ per la formazione di legami carbonio-azoto e carbonio-ossigeno. Inoltre, intende sviluppare un protocollo catalitico di nitrazione degli alogenuri arilici usando NO₂ sia come ossidante che come fonte di azoto. Infine, prevede di sviluppare complessi nichel-NO₂ attivati fotochimicamente per la scissione ossidativa degli alcheni, come alternativa più sicura e meglio controllata all’ozono.

Obiettivo

Nitrogen dioxide (NO2) is a reactive combustion by-product with untapped potential as a synthetic reagent. Unlike traditional nitrogen sources used in catalysis, NO2 is a persistent radical capable of unique one-electron pathways, yet its use in controlled bond-forming reactions remains virtually unexplored. NOVa [Nitrogen(IV) Oxide Valorisation] proposes to harness this reactivity by developing catalytic methods that transform NO2 into nitroarenes and carbonyl compounds through Ni-catalysed radical processes.

The project aims to develop a suite of Ni-catalysed transformations that exploit the open-shell reactivity of NO2 to forge C–N and C–O bonds under mild conditions. Stoichiometric studies will be used to intercept and characterise key Ni(III) intermediates formed via radical capture, shedding light on the mechanisms of high-valent reductive elimination. These insights will guide the development of a catalytic aryl halide nitration, using NO2 as both oxidant and nitrogen source. Finally, photochemically activated Ni– NO2 complexes will be designed to mimic ozone in the oxidative cleavage of alkenes, offering a safer and more tunable platform for oxygen-transfer chemistry. Collectively, these transformations will deliver atom-economical routes to valuable nitrogen and oxygen functionalities, while advancing new reactivity modes for persistent radicals and deepening understanding of key organometallic intermediates.

Through training at ICIQ in the group of Prof. Rubén Martín, the researcher will gain experience in radical-based catalysis, mechanistic analysis of Ni-mediated transformations, and the development of methodologies that operate under mild and sustainable conditions. This research environment will support the researcher's progression toward an independent career through exposure to frontier topics, interdisciplinary collaboration, and high-level scientific communication.