Charge Separation – A General Motif for the Activation and Catalytic Functionalization of Strong Bonds

Informations projet

PUSH-IT

N° de convention de subvention: 948185

DOI

10.3030/948185

Projet clôturé

Date de signature de la CE 11 Septembre 2020

Date de début 1 Decembre 2020

Date de fin 31 Mai 2026

Financé au titre de

• EXCELLENT SCIENCE - European Research Council (ERC)

Coût total

€ 1 499 658,00

Contribution de l’UE

€ 1 499 658,00

Coordonné par

UNIVERSITAT DES SAARLANDES
Germany

Periodic Reporting for period 3 - PUSH-IT (Charge Separation – A General Motif for the Activation and Catalytic Functionalization of Strong Bonds)

Période du rapport: 2023-12-01 au 2025-05-31

Résumé du contexte et des objectifs généraux du projet

This research project targets molecules with a multiple bond between a metal and a ligand. Such compounds are believed to be the key-ingredients in oxidation catalysis. Examples include thereby the catalytic converters in automotives or the production of nitric acid, which ranks among the most important industrial chemical processes. Additionally, such compounds are believed to be of use for the valorization of fine-chemicals as is required, among others, in the pharmaceutical- and polymer industries.
So far, such compounds with multiple bonds largely eluded isolation, and the electronic structure of these alleged intermediates remains unclear. This prevents the non-empirical design of novel classes of catalysts, which is the major obstacle for future applications. In contrast, isolating such fleeting intermediates in molecular form in the laboratory and studying their physical and chemical properties will allow to deliberately design new generations of catalysts with largely enhanced activity, affordability, and sustainability. As such, this fundamental research project targets in the mid-to-long term the implementation of cleaner and more affordable chemical transformations on both large- and small- industrial scale.

Travail effectué depuis le début du projet jusqu’à la fin de la période considérée dans le rapport et principaux résultats atteints jusqu’à présent

We have targeted terminal oxides, phosphinidenes, carbynes, carbides and nitrenes of various metals of the s-, p- and d-block. So far, we succeeded in isolating and studying phosphinidenes, imides, nitrenes and carbenes/carbynes. Applications in functional group transfer and catalysis are ongoing, and the metalation of strong CH-bonds has been demonstrated. We have developed novel supporting ligand systems with hitherto unprecedented stability, and have quantified their radical-stabilization capabilities. Somehow unexpected, we serendipitously discovered a new type of metalloid cluster, which may serve as materials for optoelectronic applications. Accordingly, and likewise initially unexpected, we discovered a new entry towards organic-electronic materials based on our ancillary ligands. Further, we discovered a new class of phosphino-nitrenoid compounds of relevance in small-molecule activation.

Progrès au-delà de l’état des connaissances et impact potentiel prévu (y compris l’impact socio-économique et les conséquences sociétales plus larges du projet jusqu’à présent)

We have discovered the first anionic terminal imides of late transition metals, an unprecedented p-block carbyne, as well as the arguably first example for a coordinatively unsaturated and well-defined metalloid based on palladium. Further, we have demonstrated hitherto unprecedented applications in functional group transfer with strong bonds. Until the end of the project, we additionally expect the (i) discovery of nitrenes, (ii) of further terminal carbyne/carbide complexes, and (iii) umpolung in main-group compounds with multiple bonds. Further, we will implement unprecedented catalytic cycles with strong bonds. Based on the various serendipitous and exciting findings outlined above, we further envisage N2 activation chemistry with phosphorus as well as the development of opto-electronic materials based on organic- and metalloid building blocks.

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