Project description
Bismuth compounds make their mark on catalysis
The classical distinction between transition metal and main group compounds is starting to blur. Researchers are increasingly recognising that main group elements could even outperform transition metals in catalysis. Bismuth, a main group element surrounded by toxic elements in the periodic table, has been overlooked as a possible reagent. Bismuth is a non-precious, non-toxic, heavy p-block element. Its large and diffuse atomic orbitals result in an inefficient overlap with the orbitals of other atoms, leading to low homolytic bond dissociation energies. The main goal of the EU-funded Bismuth Goes Radical project is to design new methods for synthesising bismuth compounds with unique properties and unlock their tremendous potential in synthetic chemistry.
Objective
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.
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ERC-STG - Starting GrantHost institution
35037 Marburg
Germany