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HEIndividual fellowship2023–2025

RATIO · Rationally-designed Turbo reagents for Innovative Organometallics

Horizon Europe — Marie Skłodowska-Curie Actions

Duration
2023-07-01 → 2025-06-30
EU contribution
€210,911
Participants
2
Scheme
HORIZON-TMA-MSCA-PF-EF

Lines connect the coordinator with its partners.

Results in brief

Rationally-designed Turbo reagents for Innovative Organometallics

Organic magnesium compounds, alias Grignard reagents, are inexpensive and mostly non-toxic polar reagents used to create new carbon-carbon bonds. Such features are ideal for the preparation of a wide variety of chemicals, like drug synthesis and soil-enriching fertilizers, making these molecules indispensable reagents in modern organic chemistry processes in academic laboratories and industries. Although commonly widespread, an even larger use of these reagents is hampered by their very low tolerance of protic solvents and their variable selectivity. Therefore, systematic improvements of these reagents are essential to empower chemists with low-cost and environmentally friendly new synthetic tools. A major discovery to enhance these reagents was made by adding lithium salts to the mixture, which improved both the reactivity and selectivity (turbo-Grignard). Moreover, the possibility to work in a non-miscible mixture of organic and green deep eutectic solvent (DES), asserted the opportunity for a more sustainable chemistry and prompted further studies that focus on the key role of these non-standard solvents. An exhaustive study is required to face the evidence that numerous species coexist in solution, and that reactivity and abundance are not necessarily correlated. The project wants to understand the structure and reactivity of organomagnesium reagents and the effect of lithium salts in organic and organic/DES mixed solvents, tailoring a strategy based on all-atom reactive molecular dynamics. We want to study the structure of archetypal reagents in explicit solvent to elucidate the composition of such solutions, which is currently unknown. The results will be used to simulate carbon-carbon bond formation reactions, with the objective of obtaining the mechanism and energetics of such processes. Thus, it will be possible to apply rational design to the reactants to improve their reactivity and selectivity. Finally, a different area will be investigated, namely the reactivity of these molecules in mixed phases to unveil the beneficial effects of the added deep eutectic solvent.

Data: CORDIS, © European Union

Project objective

This project aims to study the structure, dynamics, and reactivity of prominent alkali and alkaline-earth organometallics species by ab initio and multi-scale computational approaches. Main group organometallic compounds are cheap and mostly non-toxic; therefore, they are appealing to industrial processes and are employed today in an ever-growing list of reactions, including drug synthesis or fertilizer manufacturing. In fact, little is known about their molecular structures in solution and the mechanisms by which they react, hampering the development of more efficient reagents or experimental conditions. This is due to their highly fluxional nature, yielding a diversity of structures in fast equilibria controlled by the solvent. Ab initio molecular dynamics offers the best way to investigate these systems, as demonstrated by recent studies unveiling the structure of a pure Grignard reagent and its reaction with carbonyl substrates in a THF solution (Peltzer et al, JACS 2020). This project expands the horizon over considerably more challenging and intriguing members of the Grignard family, formed by mixing metals species or solvents, which show unexplained synergistic effects on reactivity and selectivity. First, the project will characterize the structures and reactivity (Mg-C bond formation) of mixed Mg/Li turbo-Grignard and turbo-Hauser reagents in solvent. Then, attention will be drawn on the recently discovered remarkable synergy produced by running the Grignard reaction in non-miscible mixture of organic and green deep eutectic solvents. By understanding the role of the mixed solvents for these reactions, the project aims to open the route for the design of cheaper and environmentally friendly experimental conditions. The project, carried out in collaboration with an international experimental leader will have a great positive impact on the applicant's career identifying him as one of the key players in the development of green efficient main group chemistry.

Original text from CORDIS.

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Data: CORDIS, © European Union