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Bis(oxazoline)-Derived N-Heterocyclic Carbene Ligated Rare-Earth Metal Complexes: Synthesis, Structure, and Polymerization Performance

Abstract

Bis(oxazoline)-derived N-heterocyclic carbene (IBiox) supported rare-earth (Sc, Y, Lu) trialkyl complexes have been synthesized and structurally characterized, and their catalytic activity in the (co)polymerization of α-olefins has been studied. The treatment of Ln(CH2SiMe3)3(THF)2 with one equivalent of freshly prepared IBiox afforded the rare-earth metal complexes (IBiox)Ln(CH2SiMe3)3THFn (Ln = Sc (1), n = 0; Y (2), n = 1; Lu (3), n = 1) in good yields. Single crystal X-ray diffraction study showed that 1 is pseudo tetrahedral, while 2 and 3 are distorted trigonal bipyramidal with coordinated THF. The Ln-C(carbene) bond distances in 1, 2, and 3 are 2.352, 2.550 and 2.479 Å, respectively. DFT calculations were conducted to study the bonding scheme and structural stability. Complex 1 showed high activity for 1-hexene polymerization by activation with 2 equivalents of [Ph3C][B(C6F5)4], and the resultant polymers are with predominate vinylene end groups (ca. 95 %). Moreover, the catalyst system based on 1 proved to be effective on copolymerization of 1-hexene with 1,7-octadiene affording the copolymers with about 20% pendant vinyl groups. The hydrophilicity of copolymers was improved by modifing the vinyl groups with carboxyls via thiol-ene reaction.

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Publication details

The article was received on 24 May 2018, accepted on 10 Jul 2018 and first published on 11 Jul 2018


Article type: Paper
DOI: 10.1039/C8DT02130A
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Bis(oxazoline)-Derived N-Heterocyclic Carbene Ligated Rare-Earth Metal Complexes: Synthesis, Structure, and Polymerization Performance

    Y. Pan, A. Zhao, Y. Li, W. Li, Y. SO, X. Yan and G. He, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT02130A

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