Catalytic activation of remote alkenes through silyl-rhodium(III) complexes Prieto Pascual, Unai Choquesillo Lazarte, Duane Rodríguez Diéguez, Antonio The tandem isomerization–hydrosilylation reaction is a highly valuable process able to transform mixtures of internal olefins into linear silanes. Unsaturated and cationic hydrido-silyl-Rh(III) complexes have proven to be effective catalysts for this reaction. Herein, three silicon-based bidentate ligands, 8-(dimethylsilyl) quinoline (L1), 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3), have been used to synthesize three neutral [RhCl(H)(L)PPh3] (1-L1, 1-L2 and 1-L3) and three cationic [Rh(H)(L) (PPh3)2][BArF 4] (2-L1, 2-L2 and 2-L3) Rh(III) complexes. Among the neutral compounds, 1-L2 could be characterized in the solid state by X-ray diffraction showing a distorted trigonal bipyramidal structure. Neutral complexes (1-L1, 1-L2 and 1-L3) failed to catalyze the hydrosilylation of olefins. On the other hand, the cationic compound 2-L2 was also characterized by X-ray diffraction showing a square pyramidal structure. The unsaturated and cationic Rh(III) complexes 2-L1, 2-L2 and 2-L3 showed significant catalytic activity in the hydrosilylation of remote alkenes, with the most sterically hindered (2-L2) being the most active one 2023-07-26T08:56:29Z 2023-07-26T08:56:29Z 2023-05-31 journal article Dalton Trans., 2023, 52, 9090[DOI: 10.1039/d3dt00624g] https://hdl.handle.net/10481/84010 10.1039/d3dt00624g eng http://creativecommons.org/licenses/by-nc-nd/4.0/ open access Attribution-NonCommercial-NoDerivatives 4.0 Internacional Royal Society of Chemistry