Descripción del proyecto
Aluminio abundante, benigno y rentable en catalizadores altamente reactivos
Los metales de transición son únicos en el sentido de que pueden tener electrones de valencia (electrones que pueden participar en la formación de enlaces químicos) en subcapas y no solo en la capa exterior. Dado que donan o aceptan electrones con facilidad, se utilizan ampliamente para catalizar reacciones en la química industrial y sintética. Se ha demostrado que los complejos de aluminio de valencia baja actúan como los metales de transición, lo que sugiere que el aluminio, abundante y barato, podría abrir una vía más rentable y ecológica para la activación de enlaces y la catálisis. El proyecto ALLOWE, financiado con fondos europeos, trata de explotar este potencial investigando la síntesis, el aislamiento y la reactividad de los sistemas de aluminio de valencia baja.
Objetivo
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.
Ámbito científico
Palabras clave
Programa(s)
Régimen de financiación
ERC-COG - Consolidator GrantInstitución de acogida
80333 Muenchen
Alemania