doi:10.1002/chem.202303935engTejero, Álvaro G.Castillo, JavierViguri, FernandoCarmona, DanielPassarelli, VincenzoLahoz, Fernando J.García-Orduña, PilarRodríguez, RicardoDynamic Configuration on a Chiral-at-Rhodium Catalyst Featuring a Flexible Tetradentate LigandART-2024-137135The 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 : 1.2024http://zaguan.unizar.es/record/13167110.1002/chem.202303935http://zaguan.unizar.es/record/131671oai:zaguan.unizar.es:131671info:eu-repo/grantAgreement/ES/DGA/E05-23Rinfo:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00info:eu-repo/grantAgreement/ES/MCIU/RED2018-102574-Tinfo:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00Chemistry - A European Journal 30, 10 (2024), 202303935 [6 pp.]All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess