Rare-Earth Metal Complexes Supported by 1,3-Functionalized Indolyl-Based Ligands for Efficient Hydrosilylation of Alkenes

Two different 1,3-functionalized indolyl-based proligands 1-(2-C₄H₇O)CH₂-3-(2-^tBuC₆H₅N═CH)C₈H₅N (HL¹) and 1-Me₂NCH₂CH₂-3-(2-ⁱPrC₆H₅N═CH)C₈H₅N (HL²) were designed, prepared in high yields, and successfully applied to rare-earth metal chemistry showing different reactivities and different bondings with the central metals. The reactions of HL¹ with RE(CH₂SiMe₃)₃(THF)₂ provided two types of rare-earth metal complexes: the pincer type mononuclear complexes κ³-(L¹)RE(CH₂SiMe₃)₂ [L¹ = 1-(2-C₄H₇O)CH₂-3-(2-^tBuC₆H₅N═CH)C₈H₄N, RE = Lu(1), Yb(2)], and the dinuclear rare-earth metal alkyl (per alkyl/per metal) complexes having the ligand in novel coordination modes {(η¹:(μ-η²:η¹):η¹-1-(2-C₄H₇O)CH₂-3-[2-^tBuC₆H₅NCH-(CH₂SiMe₃)]C₈H₄N)RECH₂SiMe₃}₂ [RE = Er(3), Y(4), Dy(5), and Gd(6)]. Meanwhile, the reactions of HL² with RE(CH₂SiMe₃)₃(THF)₂ led to the isolation and characterization of only the mononuclear rare-earth metal dialkyl complexes κ³-(L²)RE(CH₂SiMe₃)₂ [L² = 1-Me₂NCH₂CH₂-3-(2-ⁱPrC₆H₅N═CH)C₈H₄N, RE = Lu(7), Gd(8)] bearing the ligand in the pincer chelate form. The mononuclear complexes were formed through the sp² C-H activation of the 2-indolyl moiety, while the dinuclear complexes were produced unexpectedly through the tandem 2-indolyl sp² C-H activation and C═N insertion into the RE-CH₂SiMe₃ bond. These complexes were fully characterized by spectroscopic methods, elemental analyses, and single-crystal X-ray crystallography. The applications of the synthesized complexes as catalysts for the hydrosilylation of terminal alkenes with phenylsilane are described. Anti-Markovnikov addition products were produced by the hydrosilylation of aliphatic olefins, and Markovnikov addition products were isolated with aromatic olefins with high selectivity in the absence of cocatalysts. It is found that the dinuclear rare-earth alkyl complexes exhibited the best catalytic activity with the advantages of mild reaction conditions, short reaction time, low catalyst loading, and wide substrate applicability in comparison with the synthesized mononuclear complexes and the reported catalysts.