Catalytic activation of remote alkenes through silyl-rhodium(III) complexes
Metadatos
Afficher la notice complèteEditorial
Royal Society of Chemistry
Date
2023-05-31Referencia bibliográfica
Dalton Trans., 2023, 52, 9090[DOI: 10.1039/d3dt00624g]
Patrocinador
PID2019-111281GB-I00; MCIN/AEI/10.13039/501100011033; IT1741-22 and IT1553-22; Gobierno Vasco; SGiker for technical and human support. Universidad del País Vasco (UPV/EHU); IKERBASQUERésumé
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