Resumen: The unique dynamic configuration of an enantioselective chiral‐at‐metal catalyst based on Rh(III) and a non‐chiral tetradentate ligand is described and resolved. At room temperature, the catalyst undergoes a dynamic configuration process leading to the formation of two interconvertible metal‐stereoisomers, remarkably without racemization. Density functional theory (DFT) calculations indicate that this metal‐isomerization proceeds via a concerted transition state, which features a trigonal bipyramidal geometry stabilized by the tetradentate ligand. Furthermore, the resolved enantiopure complex shows high catalytic enantioinduction in the Friedel‐Crafts reaction, achieving enantiomeric ratios as high as 99 : 1. Idioma: Inglés DOI: 10.1002/chem.202303935 Año: 2024 Publicado en: Chemistry - A European Journal 30, 10 (2024), 202303935 [6 pp.] ISSN: 0947-6539 Factor impacto SCIMAGO: 1.058 - Chemistry (miscellaneous) (Q1) - Organic Chemistry (Q1) - Catalysis (Q2)