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Radical NO2: Unlocking Nitrogen and Oxygen Transfer via Nickel Catalysis

Objective

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.

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Keywords

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Programme(s)

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Topic(s)

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Funding Scheme

Funding scheme (or “Type of Action”) inside a programme with common features. It specifies: the scope of what is funded; the reimbursement rate; specific evaluation criteria to qualify for funding; and the use of simplified forms of costs like lump sums.

HORIZON-TMA-MSCA-PF-EF - HORIZON TMA MSCA Postdoctoral Fellowships - European Fellowships

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Call for proposal

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(opens in new window) HORIZON-MSCA-2025-PF

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Coordinator

FUNDACIO INSTITUT CATALA D'INVESTIGACIO QUIMICA
Net EU contribution

Net EU financial contribution. The sum of money that the participant receives, deducted by the EU contribution to its linked third party. It considers the distribution of the EU financial contribution between direct beneficiaries of the project and other types of participants, like third-party participants.

€ 194 074,56
Address
AVENIDA PAISSOS CATALANS 16
43007 TARRAGONA
Spain

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Region
Este Cataluña Tarragona
Activity type
Research Organisations
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Total cost

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