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Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts

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    Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts
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    † Department of Chemistry, Center for Sustainable Polymers, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
    ‡ The School of Chemistry, Tel Aviv University, Ramat Aviv, Tel Aviv 69978, Israel
    *C.J.C.: e-mail, [email protected]; Twitter, @ChemProfCramer.
    *M.K.: e-mail, [email protected]
    *W.B.T.: e-mail, [email protected]; Twitter, @WBTolman.
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 22, 14366–14372
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    https://doi.org/10.1021/acs.inorgchem.7b02544
    Published November 8, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    The ring-opening transesterification polymerization (ROTEP) of rac-lactide (rac-LA) using LXZn catalysts (LX = ligand having phenolate, amine, and pyridine donors with variable para substituents X on the bound phenolate donor; X = NO2, Br, t-Bu, OMe) was evaluated through kinetics experiments and density functional theory, with the aim of determining how electronic modulation of the ligand framework influences polymerization rate, selectivity, and control. After determination that zinc-ethyl precatalysts required 24 h of reaction with benzyl alcohol to convert to active alkoxide complexes, the subsequently formed species proved to be active and fairly selective, polymerizing up to 300 equiv of rac-LA in 6–10 min while yielding isotactic (Pm = 0.72–0.78) polylactide (PLA) with low dispersities: Đ = 1.06–1.17. In contrast to previous work with aluminum catalysts for which electronic effects of ligand substituents were significant (Hammett ρ = +1.2–1.4), the LXZn systems exhibited much less of an effect (ρ = +0.3). Density functional calculations revealed details of the initiation and propagation steps, enabling insights into the high isotacticity and the insensitivity of the rate on the identity of X.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b02544.

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    CCDC 1577971 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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    Cited By

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    This article is cited by 38 publications.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2017, 56, 22, 14366–14372
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.7b02544
    Published November 8, 2017
    Copyright © 2017 American Chemical Society
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