Unsaturated chiral-only-at-metal rhodium(III) complexes bearing SiN-type ligands.

Enantiopure chiral-at-metal rhodium(III) unsaturated 16e complexes have been obtained from racemic [Rh(SiN)Cl] (SiN= 8-(dimethylsilyl)quinoline) using a readily accessible chiral spiroborate as chiral resolution agent. This strategy allows an easy access to enantiopure neutral Δ/Λ-Rh(SiN)2Cl and cationic Δ/Λ-Rh(SiN)2[BAr4F] unsaturated complexes, wherein rhodium(III) is coordinated to two inert silylquinoline ligands in a propeller-like arrangement.

Catalytic activation of remote alkenes through silyl-rhodium(III) complexes.

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)PPh] (1-L1, 1-L2 and 1-L3) and three cationic [Rh(H)(L)(PPh)][BAr] (2-L1, 2-L2 and 2-L3) Rh(III) complexes.

Tailor-Made Synthesis of Hydrosilanols, Hydrosiloxanes, and Silanediols Catalyzed by di-Silyl Rhodium(III) and Iridium(III) Complexes.

Siloxanes and silanols containing Si-H units are important building blocks for the synthesis of functionalized siloxane materials, and their synthesis is a current challenge. Herein, we report the selective synthesis of hydrosilanols, hydrosiloxanes, and silanodiols depending on the nature of the catalysts and the silane used. Two neutral ({MCl[SiMe(-CHPPh)]}; M = Rh, Ir) and two cationic ({M[SiMe(-CHPPh)](NCMe)}[BAr]; M = Rh, Ir) have been synthesized and their catalytic behavior toward hydrolysis of secondary silanes has been described.