cis-1,4-Polymerization of isoprene catalyzed by rare-earth metal amido complexes supported by 2-t-butylimino- or 2-amino-functionalized indolyl ligand

Feng, Zhijun; Wang, Shaoyin; Wu, Yinyin; Zhao, Xu; Wang, Xiangrui; Wang, Shaowu

doi:10.1016/j.inoche.2020.108195

Cited by 6 publications

(1 citation statement)

References 49 publications

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“…The sharp singlet signals at δ = 0.17 ppm and δ = 8.58 ppm are assigned to the resonances of the CH 2 (SiCH 3 ) 2 groups and CHN, respectively. In the 13 C NMR spectrum of 7 , the 2-indolyl sp 2 carbanion were found to resonate at δ 211.36 ppm, which are similar to those in related indolyl-based rare-earth metal complexes. ,− …”

Section: Resultsmentioning

confidence: 71%

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

Zhu

Hong

et al. 2022

Inorg. Chem.

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Two different 1,3-functionalized indolyl-based proligands 1-(2-C 4 H 7 O)CH 2 -3-(2-t BuC 6 H 5 N�CH)C 8 H 5 N (HL 1 ) and 1-Me 2 NCH 2 CH 2 -3-(2-i PrC 6 H 5 N�CH)C 8 H 5 N (HL 2 ) 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 HL 1 with RE(CH 2 SiMe 3 ) 3 (THF) 2 provided two types of rare-earth metal complexes: the pincer type mononuclear complexes κ 3and the dinuclear rare-earth metal alkyl (per alkyl/per metal) complexes having the ligand in novel coordination modes {(η 1 :(μ-η 2 :η 1 ): 4), Dy(5), and Gd( 6)]. Meanwhile, the reactions of HL 2 with RE(CH 2 SiMe 3 ) 3 (THF) 2 led to the isolation and characterization of only the mononuclear rare-earth metal dialkyl complexes κ 3 -(L 2 )RE(CH 2 SiMe 3 ) 2 [L 2 = 1-Me 2 NCH 2 CH 2 -3-(2-i PrC 6 H 5 N�CH)C 8 H 4 N, RE = Lu(7), Gd(8)] bearing the ligand in the pincer chelate form. The mononuclear complexes were formed through the sp 2 C−H activation of the 2-indolyl moiety, while the dinuclear complexes were produced unexpectedly through the tandem 2-indolyl sp 2 C−H activation and C�N insertion into the RE− CH 2 SiMe 3 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.

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Section: Resultsmentioning

confidence: 71%

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

Zhu

Hong

et al. 2022

Inorg. Chem.

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Rare-earth metal complexes supported by indolyl-based NCN-pincer ligand and their efficient catalysis for isoprene polymerization

Chu

Wang

Huang

et al. 2023

Journal of Molecular Structure

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Synthesis and Characterization of Rare-Earth Metal Complexes Bearing a 2-N,N-Dimethylamino-Ethylene-Imino-Functionalized Indolyl Ligand and Their Catalytic Activities Toward Hydrosilylation of Imines

et al. 2022

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The reactions of 2-N,N-dimethylamino-ethylene-imino-functionalized indolyl proligand 2-(Me 2 NCH 2 CH 2 N = CH)C 8 H 5 NH (HL) with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 in toluene afforded a series of rare-earth metal amido complexes [κ 3 -(N,N,N)-2-(Me 2 NCH 2 CH 2 N = CH)C 8 H 5 N]RE[N(SiMe 3 ) 2 ] 2 (RE = Y (1a), Nd (1b), Sm (1c), Gd (1d), Dy (1e), Er (1f), and Yb (1g)). While the reaction of HL with [(Me 3 Si) 2 N] 3 Eu(μ-Cl)Li(THF) 3 produced the europium(II) complex in a dimeric form [{(η 5μ-η 1 :η 2), which is believed to have happened through the homolysis of the Eu−N bond. Further reaction of complex 1a with PhCH�NPh provided an unexpected rare-earth metal complex [κ 2 -(N,N)-PhN{PhCH(CH 2 SiMe 2 )}N(SiMe 3 )]YL (7) through the sp 3 C−H bond activation of the methyl on the silicon atom to form a Y−C bond followed by the insertion of the C�N bond of the imine PhCH�NPh to form an amido group connected to the central metal. All complexes were characterized by spectroscopic methods, elemental analyses, and single-crystal X-ray diffraction, and complexes 1a−1c and 7 were additionally characterized by NMR spectroscopy. The catalytic performance of complexes 1a−1g for the hydrosilylation of imines was investigated, and the catalytic mechanism was proposed based on the experimental results.

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cis-1,4-Polymerization of isoprene catalyzed by rare-earth metal amido complexes supported by 2-t-butylimino- or 2-amino-functionalized indolyl ligand

Cited by 6 publications

References 49 publications

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

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

Rare-earth metal complexes supported by indolyl-based NCN-pincer ligand and their efficient catalysis for isoprene polymerization

Synthesis and Characterization of Rare-Earth Metal Complexes Bearing a 2-N,N-Dimethylamino-Ethylene-Imino-Functionalized Indolyl Ligand and Their Catalytic Activities Toward Hydrosilylation of Imines

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