Descripción del proyecto
Los compuestos a base de bismuto dejan su huella en la catálisis
La distinción clásica entre los metales de transición y los compuestos del grupo principal empieza a difuminarse. Los investigadores reconocen cada vez más que los elementos del grupo principal podrían llegar incluso a sobrepasar las capacidades de los metales de transición en lo relativo a la catálisis. El bismuto, un elemento del grupo principal rodeado de elementos tóxicos en la tabla periódica, ha recibido muy poca atención como posible reactivo. Se trata de un elemento pesado del bloque p, no precioso y no tóxico. Sus orbitales atómicos, grandes y difusos dan lugar a un solapamiento ineficaz con los orbitales de otros átomos, lo que genera bajas energías de disociación del enlace homolítico. El objetivo principal del proyecto Bismuth Goes Radical, financiado con fondos europeos, es diseñar nuevos métodos para sintetizar compuestos de bismuto con propiedades únicas y liberar su gran potencial para la química sintética.
Objetivo
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.
Ámbito científico
Palabras clave
Programa(s)
Régimen de financiación
ERC-STG - Starting GrantInstitución de acogida
35037 Marburg
Alemania