doi:10.1002/chem.202404657engGómez-España, AlejandraPadilla, MarinaMartínez de Morentin, AitorGarcía-Orduña, PilarHuertos, Miguel A.Munarriz, JulenFernández-Alvarez, Francisco J.Rhodium(III)-NSi Catalyzed Styrene Hydrosilylation: Evidence of the Hemilabile Character of NSi-Type LigandsART-2025-142807The 18e saturated rhodium(III) species [Rh(H)(X)(κ2‐NSitBu2)(bipyMe2)] (NSitBu2={4‐methylpyridine‐2‐yloxy}ditertbutylsilyl; bipyMe2=4,4'‐dimethylbipyridine) (X=Cl, 1; OTf, 2) have been prepared and characterized by NMR spectroscopy and in the case of 2 it has been possible to determine its solid‐state structure by X‐ray diffraction. Complex 1 has proven to be an effective catalyst precursor for the reaction of styrene derivatives with hydrosilanes in CD2Cl2. However, under catalytic conditions complex 2 decomposes. The performance of the 1‐catalyzed reaction of styrene with hydrosilanes strongly depends on the nature of the silane, the best catalytic performance was achieved using HSiMe2Ph. Theoretical and 1H NMR studies indicate that the hemilabile nature of the NSi ligand is key to understanding the catalytic activity of compound 1.2025http://zaguan.unizar.es/record/15069010.1002/chem.202404657http://zaguan.unizar.es/record/150690oai:zaguan.unizar.es:150690info:eu-repo/grantAgreement/ES/DGA/E42-23Rinfo:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00info:eu-repo/grantAgreement/ES/MICINN/PID2023-148113OB-I00info:eu-repo/grantAgreement/ES/UZ/JIUZ-2023-CIE-10Chemistry - A European Journal 31, 13 (2025), e202404657 [9 pp.]All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess