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Toolbox of Nonmetallocene Lanthanides: Multifunctional Catalysts in Group-Transfer Polymerization

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    Toolbox of Nonmetallocene Lanthanides: Multifunctional Catalysts in Group-Transfer Polymerization
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    † ‡ †WACKER-Lehrstuhl für Makromolekulare Chemie, §Chair of Theoretical Chemistry, and ‡Department Chemie & Catalysis Research Center, Technische Universität München, 85748 Garching bei München, Germany
    *E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 16, 9754–9764
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    https://doi.org/10.1021/acs.inorgchem.7b01261
    Published August 10, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    Herein, we present a fundamental study of isostructural 2-methoxyethylamino-bis(phenolate)-lanthanide complexes [(ONOO)RM(X)(THF)] (M = Lu, Y; R = tBu, CMe2Ph, X = CH2TMS, collidine; THF = tetrahydrofuran; TMS = trimethylsilyl) for rare-earth metal-mediated group-transfer polymerization (GTP). This analysis includes the differentiation of electron-donating and nondonating vinyl monomers and two metal centers with regard to the ionic radius (yttrium and lutetium). In addition, highly nucleophilic alkyl initiators are compared with electron-donating heteroaromatic initiators. Our examinations include the impact of these parameters on the activity, initiator efficiency, and tacticity of the obtained polymers. Density functional theory calculations and proposed catalyst structure determinations via X-ray analysis support these investigations. This facilitates the selection of the best metal and initiator combination to address efficient and stereospecific polymerization of a broad range of Michael monomers. [(ONOO)tBuLu(X)(THF)] shows the highest activity of 2220 h–1 (normalized turnover frequency) for the polymerization of 2-vinylpyridine due to the higher Lewis-acidity of lutetium. Through C(sp3)–H bond activation, catalysts with higher initiator efficiency in N,N′-dimethylacrylamide (DMAA) and diethylvinylphosphonate polymerization were synthesized. Remarkably, [(ONOO)tBuY(collidine)(THF)] was capable of stereospecifically polymerizing DMAA to highly isotactic poly(DMAA) (Pm = 0.94). Overall, the kinetics studies reveal a living-type GTP mechanism for all of the tested catalysts, enabling precise molecular-weight predeterminations with narrow molecular weight distributions (Đ ≤ 1.06).

    Copyright © 2017 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01261.

    • Experimental section, further analytic data, DFT calculations, X-ray data (CCDC 1547971), and polymer characteristics (PDF)

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    CCDC 1547971 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cite this: Inorg. Chem. 2017, 56, 16, 9754–9764
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.7b01261
    Published August 10, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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