Innovative alkaline earth systems for the activation and functionalization of dinitrogen and other challenging substrates

Project Information

AE-FUN

Grant agreement ID: 101108798

DOI

10.3030/101108798

Project closed

EC signature date 6 April 2023

Start date 1 June 2023

End date 31 May 2025

Funded under

• Marie Skłodowska-Curie Actions (MSCA)

Total cost

No data

EU contribution

€ 172 018,56

Coordinated by

AGENCIA ESTATAL CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS
Spain

Periodic Reporting for period 2 - AE-FUN (Innovative alkaline earth systems for the activation and functionalization of dinitrogen and other challenging substrates)

Reporting period: 2024-06-01 to 2025-05-31

Summary of the context and overall objectives of the project

Catalysis has been recognized as a critical tool of contemporary society. However, there are still many limitations of current catalytic methods. For example, ammonia production relies upon the highly energy-intensive Haber-Bosch process, which consumes up to 3% of the global energy produced annually. For this reason, developing new catalytic systems that achieve this transformation in milder conditions are highly desirable.
This EU-funded AE-FUN project aims to develop novel systems based on earth-abundant alkaline earth metals for the challenging conversion of dinitrogen into ammonia and other nitrogen-containing valuable chemicals. We seek to establish the grounds for a promising approach to sustainable catalysis by exploring for the partnership between abundant alkaline earth (Ae) metals in low oxidation states and transition metals (TM). We envisioned that by harnessing the unexplored modes of cooperativity between TM and low-valent Ae metals, new synergies will arise and facilitate the activation of challenging substrates and their functionalization.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

During this period, a series of novel alkaline-earth complexes bearing bulky neutral or anionic ligands have been synthesized. These complexes show great stability towards Schlenk equilibrium, a well-known process which poses an additional difficulty to the obtention of well-defined heteroleptic alkaline-earth complexes. Some of these complexes contain halide groups which make them useful precursors for reactivity and catalysis. These new Ae complexes were characterized by various spectroscopic techniques, including single-crystal x-ray structure determination.
Depending on the ligand framework used, a family of mono-, bi- or polynuclear complexes are obtained. In addition, for a same ligand, the geometry of the resulting complex can also depend on the nature of the Ae metal (Mg gives the potassium ‘ate’ complex, Ca forms dimers; and Sr and Ba form polynuclear clusters).

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

During our investigations, in our search for new compounds suitable for the stabilization of low-valent metals, we developed a new series of ligand precursors. In addition, we found that one of these compounds can promote the activation of highly stable aromatic bonds. This ground-breaking result is a major accomplishment and may find a wide range of applications for the activation of strong bonds.