Bis(carbene) Analogues of Aluminium and Gallium as Building Blocks for Highly Selective Reagents and Next Generation Catalysts

Projektbeschreibung

Effiziente und nachhaltige chemische Synthese mit Bis(carben)-Analoga von Aluminium und Gallium

Aktuelle Synthesemethoden in der Molekularchemie basieren häufig auf teuren Edelmetallen oder werden durch nicht übereinstimmende Molekülorbitale beeinträchtigt, was zur Entstehung von Abfall und unerwünschten Nebenprodukten führt. Darüber hinaus bestehen Sicherheitsbedenken hinsichtlich der Toxizität der Reagenzien und der Erzeugung gefährlicher Abfälle. Das ERC-finanzierte Projekt AGILE zielt darauf ab, diese Probleme durch die Entwicklung neuartiger nachhaltiger Synthesemethoden zum Aufspalten und Bilden chemischer Bindungen sowie zur Redoxkatalyse mit einem einzigen System anzugehen. Zu diesem Zweck wird die Verwendung von Bis(carben)-Analoga von Aluminium und Gallium vorgeschlagen, deren einzigartige Grenzmolekülorbitale eine reversible Reaktivität ermöglichen. Dies ebnet den Weg für eine bessere Kontrolle und Modulation von Reaktionsprozessen, was wiederum in atomökonomischen Reaktionswegen, Abfallreduzierung, Kosteneffizienz und geringerer Umweltbelastung resultiert.

Ziel

Molecular chemistry impacts on a wide range of transformational activities that the society relies on and thus plays a key role in addressing the societal challenges facing the European Union in the 21st century. Current synthetic methods commonly depend on rare and costly precious metals or face obstacles stemming from mismatching molecular orbitals, which necessitates atom-inefficient synthetic pathways. Hence, research on the utilisation of abundant and environmentally benign elements in synthesis and catalysis and the exploration of alternative activation and functionalisation strategies is urgently required.
AGILE addresses these challenges by establishing new methods for breaking and making chemical bonds and for redox-catalysis with a single system, i.e. homo- and heterobimetallic bis(carbene) analogues of aluminium and gallium, which will be utilised as the next generation of selective reagents, high performing catalysts, and valuable ligands.
AGILE will develop novel, reactive compounds that combine the benefits of derivatives in highly reactive oxidation states with the cooperativity of dinuclear Al and Ga complexes that are cheap, environmentally benign, and non-toxic. Equipped with unique frontier molecular orbitals, they will provide the reversible reactivity crucially required to unlock a wide range of elemental steps. By merging two one-electron processes, AGILE will overcome the limitations of monometallic two-electron reactions, thereby enabling redox-catalysis by main-group bimetallics. Finally, AGILE will use prototypical Lewis-acids as very strong electron donors to promote redox-catalysis with abundant first-row transition metals. In-depth kinetic, spectroscopic, and computational insight will help us achieve these challenging objectives.
By providing new catalysts and expanding the scope of challenging chemical transformations, AGILE will significantly contribute to the development of main-group chemistry and more sustainable synthetic methods.