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HEIndividual fellowship2022–2025

NITRO-EARTH · Nitrogen Chemistry with Alkaline-Earth Metals

Horizon Europe — Marie Skłodowska-Curie Actions

Duration
2022-06-01 → 2025-10-31
EU contribution
€189,687
Participants
1
Scheme
HORIZON-TMA-MSCA-PF-EF

Lines connect the coordinator with its partners.

Results in brief

Nitrogen Chemistry with Alkaline-Earth Metals

This project investigated the nitrogen chemistry of Group 2 metals, aiming to utilize inexpensive and abundant alkaline-earth metals to develop novel metal complexes for catalytic applications. The study employed established synthetic methods for N2 activation with Ca, highly reducing Mg⁰ complexes, and recently developed low-valent nitrogen ligands (nitreones) and is complemented by DFT calculations tailored for these systems. Experimental and computational efforts were performed as planned. While trapping imide and nitride species proved challenging, we successfully synthesized and characterized new metal azide, amide, and iminato complexes and analyzed their unique reactivity patterns. This report also presents a thorough utilization of DFT methods for the prediction of potential energy surfaces of unprecedented complexes and describes an in-depth investigation of their electronic structures.

Data: CORDIS, © European Union

Project objective

NITRO-EARTH is aiming to investigate the hardly explored nitrogen chemistry of the alkaline-earth metals (Ae) in order to disclose new reactivity and catalysis. In the biogeochemical nitrogen cycle oxidized (NOx), neutral (N2) and reduced (NH3) forms of N are interconverted by a complicated network of processes. In contrast, manipulation of N in industry is challenging and often needs brute-force methods. The Haber-Bosch process for N2-to-NH3 conversion is, despite being metal-catalysed, one of the most energy consuming industrial processes. This proposal focusses on the organometallic chemistry of imido [RN(2ˉ)] and nitrido [N(3ˉ)] complexes of the alkaline-earth metals, in particular Mg and Ca. While the amide (R2Nˉ) chemistry of the Ae metals is well-established, Ae-imido complexes are rare and Ae-nitrido compounds solely exist as insoluble salts, e.g. Mg3N2. Given the importance of imido and nitrido ligands in transition metal chemistry, access to soluble Ae=NR and Ae≡N complexes promises a rich reactivity and is the prelude of new catalytic processes based on abundant, generally biocompatible, alkaline-earth metals. The various pathways to reach the target include utilization of recently introduced, highly reducing Mg(0) complexes by HARDER and nitreones which have been investigated by PATEL. Also HARDER’s recently discovered N2 fixation with Ca will play a role in the synthetic approach. Owing to the highly ionic character and negative charge on N in Ae=NR or Ae≡N complexes, these novel complexes will be extremely potent nucleophiles or deprotonating reagents. This will be strongly dependent on nuclearity and aggregation which will be controlled by a library of bulky ligands currently available in the HARDER group. The work will be heavily supported by ab initio calculations. The project ultimately leads to the generation of a new class of alkaline-earth metal catalysts which may provide sustainable alternative for transition metal based catalysts.

Original text from CORDIS.

Participants

  • FRIEDRICH-ALEXANDER-UNIVERSITAET ERLANGEN-NUERNBERG · ErlangenCoordinatorGermany

Links

Data: CORDIS, © European Union