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Perfectly isoselective polymerization of 2-vinylpyridine promoted by β-diketiminato rare-earth metal cationic complexes

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Abstract

Symmetric and asymmetric β-diketiminato rare-earth metal dialkyl complexes L1Ln(CH2SiMe3)2(THF) (L1 = (2,6-Et2C6H3)NC(Me)CHC(Me)N(2,6-Et2C6H3), Ln = Y (1a), Lu (1b)) and L2Ln(CH2SiMe3)2(THF) (L2 = (2,6-iPr2C6H3)NC(Me)CHC(Me)N(C6H5), Ln = Y (2a), Lu (2b)) have been synthesized by the reaction of the precursor Ln(CH2SiMe3)3(THF)2 with the corresponding pro-ligands (HL1 and HL2) in good yield. These complexes promote the polymerization of 2-vinylpyridine (2-VP) to produce isotactic-biased poly(2-vinylpyridine) (P2VP) (mm: 40%) in quantitative yield. The in situ generated cationic species with the addition of borate ([Ph3C][B(C6F5)4], [PhNHMe2][B(C6F5)4]) prior to the polymerization display distinct results, and the symmetric ones afford perfectly isotactic P2VP with an mm value up to 99%, whilst the asymmetric ones produce atactic P2VP (mm: 26%). The 1H NMR spectrum and MALDI-TOF mass analysis of an oligomer prepared with 1a/[Ph3C][B(C6F5)4] indicate that the polymerization is initiated by coordination insertion of 2-VP into the Y-CH2SiMe3 bond of the in situ generated cationic species.

Graphical abstract: Perfectly isoselective polymerization of 2-vinylpyridine promoted by β-diketiminato rare-earth metal cationic complexes

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Publication details

The article was received on 10 Aug 2018, accepted on 26 Sep 2018 and first published on 27 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03274B
Citation: Dalton Trans., 2018, Advance Article
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    Perfectly isoselective polymerization of 2-vinylpyridine promoted by β-diketiminato rare-earth metal cationic complexes

    Z. Mou, Q. Zhuang, H. Xie, Y. Luo and D. Cui, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT03274B

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