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Soft N-Type Functionalized Fluorenyl Ligated Rare-Earth Metal Complexes: Synthesis, Structure, and Catalytic Performance for 2-Vinylpyridine

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Abstract

A series of new N-type functionalized fluorenyl rare-earth metal complexes were synthesized. Treatment of piperidinyl- or hexamethyleneimino-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species [Ln(CH2SiMe3)2(THF)x][BPh4] afforded readily the corresponding constrained-geometry-complexes L1Ln(CH2SiMe3)2 (L1 = FluCH2CH2NC5H10, Ln = Y (1-Y), Lu (1-Lu), Sc (1-Sc)), L2Ln(CH2SiMe3)2 (L2 = (2,7-di-tert-butyl)FluCH2CH2NC5H10, Ln = Y (2-Y), Lu (2-Lu), Sc (2-Sc)) and L3Lu(CH2SiMe3)2 (L3 = (2,7-di-tert-butyl)FluCH2CH2NC6H12 (3-Lu)) in moderate yields. All these complexes were characterized by NMR spectroscopy, and the solid-state molecular structures of 1-Y and 2-Sc were defined with single-crystal X-ray diffraction analysis (CCDC nos. 2157591 (1-Y) and 2160297 (2-Sc)). The catalytic performance of these complexes towards 2-vinylpyridine polymerization was studied, where these complexes alone could efficiently promote the polymerization of 2-vinylpyridine giving isotactic poly(2-vinylpyridine). The polymerization proceeded in first-order kinetics with respect to both monomer and catalyst concentration.

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Funding

The authors acknowledge financial support from the National Natural Science Foundation of China (no. 21805143), the Natural Science Foundation of Zhejiang Province (no. LY21B040002), and the K.C. Wong Magna Fund from Ningbo University.

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Authors and Affiliations

  1. Key Laboratory of Advanced Mass Spectrometry and Molecular Analysis of Zhejiang Province, School of Materials Science and Chemical Engineering, Ningbo University, 315211, Ningbo, P.R. China

    Z. H. Mou & Y. J. Wang

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  1. Z. H. Mou
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Correspondence to Z. H. Mou.

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Mou, Z.H., Wang, Y.J. Soft N-Type Functionalized Fluorenyl Ligated Rare-Earth Metal Complexes: Synthesis, Structure, and Catalytic Performance for 2-Vinylpyridine. Russ J Coord Chem 48, 526–535 (2022). https://doi.org/10.1134/S1070328422330016

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