Radical NO2: Unlocking Nitrogen and Oxygen Transfer via Nickel Catalysis

Descripción del proyecto

Transferencia de nitrógeno y oxígeno catalizada por níquel mediante NO2

El dióxido de nitrógeno (NO2) es un radical persistente que se genera como subproducto de la combustión. Su singular reactividad monoelectrónica ofrece numerosas posibilidades para su uso como reactivo en síntesis química. El objetivo del proyecto NOVa, respaldado por las acciones Marie Skłodowska-Curie, es establecer nuevas rutas de síntesis, descubrir nuevos modos de reactividad para los radicales persistentes y mejorar la comprensión de los intermedios organometálicos. En este contexto, se estudiarán transformaciones catalizadas por níquel en condiciones suaves que aprovechen la reactividad del NO2 para formar enlaces carbono-nitrógeno y carbono-oxígeno. También se desarrollará un protocolo catalítico de nitración de haluros de arilo utilizando el NO2 como oxidante y fuente de nitrógeno. Por último, se desarrollarán complejos de níquel y NO2 activados fotoquímicamente para la escisión oxidativa de alquenos, como alternativa más segura y controlable al ozono.

Objetivo

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.