Quasi-living trans-1,4-polymerization of isoprene by cationic rare earth metal alkyl species bearing a chiral (s, s)-bis(oxazolinylphenyl)amido ligand

Hui Liu; Jianyun He; Zhanxiong Liu; Zhengguo Lin; Gaixia Du; Shaowen Zhang; Xiaofang Li

doi:10.1021/ma4005549

Quasi-living trans-1,4-polymerization of isoprene by cationic rare earth metal alkyl species bearing a chiral (s, s)-bis(oxazolinylphenyl)amido ligand

Hui Liu, Jianyun He, Zhanxiong Liu, Zhengguo Lin, Gaixia Du, Shaowen Zhang^*, Xiaofang Li

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Beijing Institute of Technology

Research output: Contribution to journal › Article › peer-review

83 Citations (Scopus)

Abstract

A series of chiral mononuclear dialkyl complexes [(S,S)-BOPA]Ln(CH ₂SiMe₃)₂ (1, 2) (BOPA = (S,S)- bis(oxazolinylphenyl)amido; Ln = Sc (1); Ln = Lu (2)) and binuclear alkyl complexes [o-(S)-OPA-C₆H₄-(CH₂SiMe ₃)C=N-CH(ⁱPr)CH₂-O]Ln(CH₂SiMe ₃)}₂ (3,4) (OPA = (oxazolinylphenyl)amine; Ln = Y (3); Ln = Tm (4)) have been synthesized in moderate yields via one-pot acid-base reactions by use of the tris(trimethylsilylmethyl) rare earth metal complexes with the chiral tridentate (S,S)-bis(oxazolinylphenyl)amine ligand. In the presence of activator with or without a small amount of AlⁱBu ₃, the dialkyl complexes 1 and 2 exhibit very high activities (up to 6.8 × 10⁵ g mol_Ln^-1 h^-1) and trans-1,4-selectivity (up to 100%) in the quasi-living polymerization of isoprene, yielding the trans-1,4-PIPs with moderate molecular weights (M _n = (0.2-1.0) × 10⁵ g/mol) and narrow molecular weight distributions (M_w/M_n = 1.02-2.66).

Original language	English
Pages (from-to)	3257-3265
Number of pages	9
Journal	Macromolecules
Volume	46
Issue number	9
DOIs	https://doi.org/10.1021/ma4005549
Publication status	Published - 14 May 2013

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@article{5e5f17c5bd094886a375eb46b40b933b,

title = "Quasi-living trans-1,4-polymerization of isoprene by cationic rare earth metal alkyl species bearing a chiral (s, s)-bis(oxazolinylphenyl)amido ligand",

abstract = "A series of chiral mononuclear dialkyl complexes [(S,S)-BOPA]Ln(CH 2SiMe3)2 (1, 2) (BOPA = (S,S)- bis(oxazolinylphenyl)amido; Ln = Sc (1); Ln = Lu (2)) and binuclear alkyl complexes [o-(S)-OPA-C6H4-(CH2SiMe 3)C=N-CH(iPr)CH2-O]Ln(CH2SiMe 3)}2 (3,4) (OPA = (oxazolinylphenyl)amine; Ln = Y (3); Ln = Tm (4)) have been synthesized in moderate yields via one-pot acid-base reactions by use of the tris(trimethylsilylmethyl) rare earth metal complexes with the chiral tridentate (S,S)-bis(oxazolinylphenyl)amine ligand. In the presence of activator with or without a small amount of AliBu 3, the dialkyl complexes 1 and 2 exhibit very high activities (up to 6.8 × 105 g molLn-1 h-1) and trans-1,4-selectivity (up to 100%) in the quasi-living polymerization of isoprene, yielding the trans-1,4-PIPs with moderate molecular weights (M n = (0.2-1.0) × 105 g/mol) and narrow molecular weight distributions (Mw/Mn = 1.02-2.66).",

author = "Hui Liu and Jianyun He and Zhanxiong Liu and Zhengguo Lin and Gaixia Du and Shaowen Zhang and Xiaofang Li",

year = "2013",

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doi = "10.1021/ma4005549",

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T1 - Quasi-living trans-1,4-polymerization of isoprene by cationic rare earth metal alkyl species bearing a chiral (s, s)-bis(oxazolinylphenyl)amido ligand

AU - Liu, Hui

AU - He, Jianyun

AU - Liu, Zhanxiong

AU - Lin, Zhengguo

AU - Du, Gaixia

AU - Zhang, Shaowen

AU - Li, Xiaofang

PY - 2013/5/14

Y1 - 2013/5/14

N2 - A series of chiral mononuclear dialkyl complexes [(S,S)-BOPA]Ln(CH 2SiMe3)2 (1, 2) (BOPA = (S,S)- bis(oxazolinylphenyl)amido; Ln = Sc (1); Ln = Lu (2)) and binuclear alkyl complexes [o-(S)-OPA-C6H4-(CH2SiMe 3)C=N-CH(iPr)CH2-O]Ln(CH2SiMe 3)}2 (3,4) (OPA = (oxazolinylphenyl)amine; Ln = Y (3); Ln = Tm (4)) have been synthesized in moderate yields via one-pot acid-base reactions by use of the tris(trimethylsilylmethyl) rare earth metal complexes with the chiral tridentate (S,S)-bis(oxazolinylphenyl)amine ligand. In the presence of activator with or without a small amount of AliBu 3, the dialkyl complexes 1 and 2 exhibit very high activities (up to 6.8 × 105 g molLn-1 h-1) and trans-1,4-selectivity (up to 100%) in the quasi-living polymerization of isoprene, yielding the trans-1,4-PIPs with moderate molecular weights (M n = (0.2-1.0) × 105 g/mol) and narrow molecular weight distributions (Mw/Mn = 1.02-2.66).

AB - A series of chiral mononuclear dialkyl complexes [(S,S)-BOPA]Ln(CH 2SiMe3)2 (1, 2) (BOPA = (S,S)- bis(oxazolinylphenyl)amido; Ln = Sc (1); Ln = Lu (2)) and binuclear alkyl complexes [o-(S)-OPA-C6H4-(CH2SiMe 3)C=N-CH(iPr)CH2-O]Ln(CH2SiMe 3)}2 (3,4) (OPA = (oxazolinylphenyl)amine; Ln = Y (3); Ln = Tm (4)) have been synthesized in moderate yields via one-pot acid-base reactions by use of the tris(trimethylsilylmethyl) rare earth metal complexes with the chiral tridentate (S,S)-bis(oxazolinylphenyl)amine ligand. In the presence of activator with or without a small amount of AliBu 3, the dialkyl complexes 1 and 2 exhibit very high activities (up to 6.8 × 105 g molLn-1 h-1) and trans-1,4-selectivity (up to 100%) in the quasi-living polymerization of isoprene, yielding the trans-1,4-PIPs with moderate molecular weights (M n = (0.2-1.0) × 105 g/mol) and narrow molecular weight distributions (Mw/Mn = 1.02-2.66).

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SN - 0024-9297

VL - 46

SP - 3257

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JO - Macromolecules

JF - Macromolecules

IS - 9

ER -

Quasi-living trans-1,4-polymerization of isoprene by cationic rare earth metal alkyl species bearing a chiral (s, s)-bis(oxazolinylphenyl)amido ligand

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