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

Projektinformationen

PUSH-IT

ID Finanzhilfevereinbarung: 948185

DOI

10.3030/948185

Projekt abgeschlossen

EK-Unterschriftsdatum 11 September 2020

Startdatum 1 Dezember 2020

Enddatum 31 Mai 2026

Finanziert unter

• EXCELLENT SCIENCE - European Research Council (ERC)

Gesamtkosten

€ 1 499 658,00

EU-Beitrag

€ 1 499 658,00

Koordiniert durch

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)

Berichtszeitraum: 2023-12-01 bis 2025-05-31

Zusammenfassung vom Kontext und den Gesamtzielen des Projekts

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.

Arbeit, die ab Beginn des Projekts bis zum Ende des durch den Bericht erfassten Berichtszeitraums geleistet wurde, und die wichtigsten bis dahin erzielten Ergebnisse

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.

Fortschritte, die über den aktuellen Stand der Technik hinausgehen und voraussichtliche potenzielle Auswirkungen (einschließlich der bis dato erzielten sozioökonomischen Auswirkungen und weiter gefassten gesellschaftlichen Auswirkungen des Projekts)

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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