Description du projet
Les composés du bismuth s’imposent en catalyse
La distinction classique entre les métaux de transition et les composés du groupe principal commence à s’estomper. Les chercheurs admettent plus volontiers que les éléments du groupe principal pourraient même surpasser les métaux de transition en catalyse. Le bismuth, un élément du groupe principal entouré d’éléments toxiques dans le tableau périodique, a été négligé en tant que réactif potentiel. Le bismuth est un élément lourd du bloc p, non précieux et non toxique. Ses orbitales atomiques larges et diffuses provoquent un chevauchement inefficace avec les orbitales d’autres atomes, ce qui conduit à de faibles énergies de dissociation des liaisons homolytiques. Le principal objectif du projet Bismuth Goes Radical, financé par l’UE, est de concevoir de nouvelles méthodes de synthèse de composés de bismuth aux propriétés uniques et de libérer leur énorme potentiel en chimie de synthèse.
Objectif
The classical distinction between transition metal and main group compounds has recently been challenged. This is due to the extraordinary properties and reactivity of low-valent and radical main group species, which chemists have begun to unveil. The development of reliable synthetic approaches to new types of low-valent main group compounds and the thorough understanding of their bonding situation, (electronic) structure, and reactivity is one of the major challenges of modern main group chemistry.
Bismuth (Bi), a non-precious, non-toxic, heavy p-block element, offers unique properties for the use in synthesis and catalysis. Its large and diffuse atomic orbitals (AOs) result in an inefficient overlap with AOs of other atoms, leading to low homolytic bond dissociation energies. Also, relativistic effects contribute to the stabilisation of Bi radical species. In combination, these effects allow for reversible homolytic bond dissociations of molecular Bi species. Due to the lack of effective strategies for the exploitation of these remarkable properties, Bi compounds remain underexplored.
This ERC proposal is designed to tackle this challenge by creating innovative methods to explore novel Bi compounds in radical reactions and unlocking their tremendous potential in synthetic chemistry. It comprises three projects: P1) Bi complexes tailored to undergo (reversible) homolytic bond dissociations, P2) novel strategies for the generation of Bi(I) species with unique (singlet vs. triplet) electronic structures, and P3) geometrically constrained complexes with Bi−Bi bonds susceptible to tuneable homolysis. The compounds targeted in P1-P3 will be exploited in novel radical reactions aimed at element–element bond formation, CH activation, small-molecule activation, and catalysis for organic synthesis.
The ERC project will benefit from the extensive experience gained by the applicant’s group in Bi chemistry. Preliminary results have been obtained for all three sub-projects.
Champ scientifique
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Programme(s)
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Régime de financement
ERC-STG - Starting GrantInstitution d’accueil
35037 Marburg
Allemagne