Descrizione del progetto
Alluminio abbondante, benigno e conveniente in catalizzatori altamente reattivi
I metalli di transizione sono unici in quanto possono avere elettroni di valenza (elettroni in grado di partecipare alla formazione di legami chimici) in sottogusci e non solo nel guscio esterno. Poiché donano o accettano facilmente elettroni, sono ampiamente usati per catalizzare reazioni nella chimica industriale e sintetica. È stato dimostrato che i complessi di alluminio a basso valore agiscono come i metalli di transizione, suggerendo che l’alluminio abbondante e poco costoso potrebbe fornire un percorso più conveniente ed ecologico per l’attivazione dei legami e la catalisi. Il progetto ALLOWE, finanziato dall’UE, prevede di sfruttare queste potenzialità grazie allo studio della sintesi, dell’isolamento e della reattività dei sistemi di alluminio a bassa valenza.
Obiettivo
This ERC-CoG 2020 proposal, ALLOWE outlines a strategy for the development of low-valent aluminium systems through their synthesis, isolation, and reactivity investigation of neutral, ambiphilic, low-valent aluminium compounds, denoted “alumylenes”. Their dimeric form “dialumenes” featuring an aluminium-aluminium double bond will also be within the scope of the project. These low-valent aluminium species are expected to provide, along with greater understanding of the fundamental behaviour of low-valent aluminium, a varied and deep reactivity profile. These highly reactive compounds will offer a cheap, sustainable and non-toxic alternative to the current transition metal-based industrial chemical processes.
The proposed scheme of work begins with the synthesis of neutral alumylenes and dialumenes, respectively. This will be achieved through the use of donor ligands (i.e. N-heterocyclic carbenes) and substituents with differing electronic and steric properties. With these compounds in hand, the reactivity towards small molecules will be investigated along with development of low-valent aluminium based catalysts. Furthermore, incorporation of transition metals into these aluminium systems will be targeted as these may possess unique and interesting properties.
Established methodologies such as reductive dehalogenation or reductive dehydrohalogenation will provide access to novel low-valent aluminium compounds bearing bulky substituents and donor ligands. The synthetic portion of the work will also be supported by theoretical calculations.
The outcome of ALLOWE will provide (i) in-depth insight and understanding into low-valent aluminium’s bonding nature, particularly emphasis laid on ambiphilic aluminium center (ii) plethora of striking reactivity towards transition metal free stoichiometric and catalytic activation of small molecules, and (iii) various potential applications in aluminium-based material chemistry.
Campo scientifico
Parole chiave
Programma(i)
Argomento(i)
Meccanismo di finanziamento
ERC-COG - Consolidator GrantIstituzione ospitante
80333 Muenchen
Germania