Low-Coordinate Bimetallics for the Catalytic Activation of Carbon Dioxide, Nitrous Oxide and Ammonia

Descrizione del progetto

Innovativi catalizzatori bimetallici cooperativi a bassa coordinazione

L’anidride carbonica (CO2), il protossido di azoto (N2O) e l’ammoniaca (NH3) sono gas economici e abbondanti che possono fornire il carbonio, l’ossigeno e l’azoto necessari per una chimica di sintesi più ecologica. Tuttavia i loro legami sono molto forti e difficili da spezzare. È urgente trovare soluzioni catalitiche innovative. Il progetto BiMetalGAS, finanziato dal CER, mira a sviluppare due famiglie di complessi eterobimetallici specificamente progettati per attivare CO2, N2O e NH3. I catalizzatori bimetallici cooperativi avranno anche ambienti a bassissima coordinazione. Ciò consentirà loro di ridurre le barriere energetiche esistenti attraverso la cooperazione metallo-metallo o introducendo percorsi alternativi basati su sinergie bimetalliche. I catalizzatori saranno inoltre altamente sintonizzabili e avranno una reattività molecolare multi-sito impossibile da ottenere con i complessi mononucleari.

Obiettivo

The catalytic conversion of carbon dioxide, nitrous oxide and ammonia poses a major challenge in modern chemistry due to the high inertness of their strong chemical bonds. These gaseous molecules are abundant and cheap. Therefore, their use as C1, O1 and N1 building blocks in synthetic chemistry entails remarkable environmental and economic advantages. Nonetheless, there are yet many limitations to meet their true synthetic potential and industrial applicability, which clearly demands innovative catalytic solutions.

In BiMetalGAS, I will develop two unique families of tailor-made heterobimetallic complexes specifically designed for the catalytic activation of carbon dioxide, nitrous oxide and ammonia.

The two types of cooperative bimetallic catalysts are: (i) highly polarized bimetallic complexes and (ii) transition metal/heavier tetrylene (Ge, Sn) compounds. The high polarization of the former and the distinct and flexible bonding of the latter, will enable the activation and cleavage of the strong bonds within CO2, N2O and NH3. Importantly, these systems will share for the first time the key feature of exceptionally low-coordination environments, a design principle mostly underdeveloped in bimetallic chemistry. This will unlock the main mechanistic bottlenecks associated to highly challenging catalytic transformations of these gaseous molecules by reducing the existing energetic barriers through metal-metal cooperation or by introducing alternative pathways based on bimetallic synergisms. Of high synthetic feasibility, the targeted catalysts will offer a range of tunable features and a landscape of multi-site molecular reactivity unattainable for mononuclear complexes.

This project will offer cutting-edge science to transform cheap and abundant, yet largely inert gaseous molecules. Through groundbreaking bimetallic synergies, BiMetalGAS will set new grounds towards a more sustainable production of large-scale commodity chemicals with broad ranging applications.