Projektbeschreibung
Mit Bismutverbindungen die Katalyse verändern
Gegenwärtig beginnt die klassische Unterscheidung zwischen Übergangsmetall- und Hauptgruppenverbindungen zu verschwimmen. In der Forschung wird immer deutlicher erkannt, dass die Hauptgruppenelemente den Übergangsmetallen in der Katalyse sogar überlegen sein könnten. Bislang wurde das Hauptgruppenelement Bismut, das im Periodensystem von toxischen Elementen umgeben ist, als mögliches Reagenz eher übersehen. Bismut ist ein unedles, ungiftiges, schweres p-Block-Element. Seine großen und diffusen Atomorbitale resultieren in einer ineffizienten Überlappung mit den Orbitalen anderer Atome. Die Folge sind niedrige homolytische Bindungsdissoziationsenergien. Das Hauptziel des EU-finanzierten Projekts Bismuth Goes Radical lautet, neue Verfahren zur Synthese von Bismutverbindungen mit einzigartigen Eigenschaften zu entwickeln und deren enormes Potenzial für die synthetische Chemie zu erschließen.
Ziel
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.
Wissenschaftliches Gebiet
Schlüsselbegriffe
Programm/Programme
Thema/Themen
Finanzierungsplan
ERC-STG - Starting GrantGastgebende Einrichtung
35037 Marburg
Deutschland