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Mechanism of Initiation Stereocontrol in Polymerization of rac-Lactide by Aluminum Complexes Supported by Indolide–Imine Ligands

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2020, 53, 5, 1809-1818
    Article

    Mechanism of Initiation Stereocontrol in Polymerization of rac-Lactide by Aluminum Complexes Supported by Indolide–Imine Ligands
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    • Anna M. Luke
      Anna M. Luke
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      NSF Center for Sustainable Polymers, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      More by Anna M. Luke
      Orcidhttp://orcid.org/0000-0001-9486-5635
    • Appie Peterson
      Appie Peterson
      Department of Chemistry, Washington University in St. Louis, Campus Box 1134, 1 Brookings Drive, St. Louis, Missouri 63130, United States
      NSF Center for Sustainable Polymers, Washington University in St. Louis, St. Louis, Missouri 63130, United States
      More by Appie Peterson
      Orcidhttp://orcid.org/0000-0002-2824-7545
    • Sina Chiniforoush
      Sina Chiniforoush
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      NSF Center for Sustainable Polymers, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      More by Sina Chiniforoush
      Orcidhttp://orcid.org/0000-0002-8428-4228
    • Mukunda Mandal
      Mukunda Mandal
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      NSF Center for Sustainable Polymers, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      More by Mukunda Mandal
      Orcidhttp://orcid.org/0000-0002-5984-465X
    • Yanay Popowski
      Yanay Popowski
      Department of Chemistry, Washington University in St. Louis, Campus Box 1134, 1 Brookings Drive, St. Louis, Missouri 63130, United States
      NSF Center for Sustainable Polymers, Washington University in St. Louis, St. Louis, Missouri 63130, United States
      More by Yanay Popowski
      Orcidhttp://orcid.org/0000-0003-1569-0035
    • Hussnain Sajjad
      Hussnain Sajjad
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
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      Orcidhttp://orcid.org/0000-0003-1283-5884
    • Caitlin J. Bouchey
      Caitlin J. Bouchey
      Department of Chemistry, Washington University in St. Louis, Campus Box 1134, 1 Brookings Drive, St. Louis, Missouri 63130, United States
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      Orcidhttp://orcid.org/0000-0003-0729-6839
    • Dimitar Y. Shopov
      Dimitar Y. Shopov
      Department of Chemistry, Washington University in St. Louis, Campus Box 1134, 1 Brookings Drive, St. Louis, Missouri 63130, United States
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      Orcidhttp://orcid.org/0000-0002-4689-4383
    • Brendan J. Graziano
      Brendan J. Graziano
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
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      Orcidhttp://orcid.org/0000-0003-1449-9255
    • Letitia J. Yao
      Letitia J. Yao
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
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      Orcidhttp://orcid.org/0000-0001-9945-558X
    • Christopher J. Cramer*
      Christopher J. Cramer
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      NSF Center for Sustainable Polymers, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      *(C.J.C.) Email: [email protected]
      More by Christopher J. Cramer
      Orcidhttp://orcid.org/0000-0001-5048-1859
    • Theresa M. Reineke*
      Theresa M. Reineke
      Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      NSF Center for Sustainable Polymers, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
      *(T.M.R.) Email: [email protected]
      More by Theresa M. Reineke
      Orcidhttp://orcid.org/0000-0001-7020-3450
    • William B. Tolman*
      William B. Tolman
      Department of Chemistry, Washington University in St. Louis, Campus Box 1134, 1 Brookings Drive, St. Louis, Missouri 63130, United States
      NSF Center for Sustainable Polymers, Washington University in St. Louis, St. Louis, Missouri 63130, United States
      *(W.B.T.) Email: [email protected]
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      Orcidhttp://orcid.org/0000-0002-2243-6409
    Other Access OptionsSupporting Information (2)

    Macromolecules

    Cite this: Macromolecules 2020, 53, 5, 1809–1818
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.0c00092
    Published February 18, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The solid state and fluxional behaviors in solution of complexes L2AlOBn and L7AlOBn (Bn = benzyl) supported by an analog of salen incorporating indolide arms connected via their 2- and 7-positions were defined by experiment and theory. The complexes catalyze the stereoselective conversion of rac-lactide (rac-LA) to isotactically enriched polylactide. A key aspect of the stereocontrol was examined through study of the initiation reactions via NMR spectroscopy, X-ray crystal structures of the ring-opened products, and theory. The results include the first unambiguous structural definition of stereocontrol in ring-opening of LA by a metal–alkoxide complex and the finding that definition of the stereochemistry of initiation by the studied system is governed thermodynamically rather than kinetically.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    Cited By

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    This article is cited by 15 publications.

    1. Appie Peterson, Rami Hador, Maren Pink, Yanay Popowski, Moshe Kol, William B. Tolman. Defining Stereochemistry in the Polymerization of Lactide by Aluminum Catalysts: Insights into the Dual-Stereocontrol Mechanism. Journal of the American Chemical Society 2022, 144 (43) , 20047-20055. https://doi.org/10.1021/jacs.2c09073
    2. Farihah M. Haque, Jacob S. A. Ishibashi, Claire A. L. Lidston, Huiling Shao, Frank S. Bates, Alice B. Chang, Geoffrey W. Coates, Christopher J. Cramer, Paul J. Dauenhauer, William R. Dichtel, Christopher J. Ellison, Ethan A. Gormong, Leslie S. Hamachi, Thomas R. Hoye, Mengyuan Jin, Julia A. Kalow, Hee Joong Kim, Gaurav Kumar, Christopher J. LaSalle, Stephanie Liffland, Bryce M. Lipinski, Yutong Pang, Riffat Parveen, Xiayu Peng, Yanay Popowski, Emily A. Prebihalo, Yernaidu Reddi, Theresa M. Reineke, Daylan T. Sheppard, Jeremy L. Swartz, William B. Tolman, Bess Vlaisavljevich, Jane Wissinger, Shu Xu, Marc A. Hillmyer. Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research. Chemical Reviews 2022, 122 (6) , 6322-6373. https://doi.org/10.1021/acs.chemrev.1c00173
    3. Christopher A. DeRosa, Anna M. Luke, Kendra Anderson, Theresa M. Reineke, William B. Tolman, Frank S. Bates, Marc A. Hillmyer. Regioregular Polymers from Biobased (R)-1,3-Butylene Carbonate. Macromolecules 2021, 54 (13) , 5974-5984. https://doi.org/10.1021/acs.macromol.1c00828
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    5. Pattarawut Sumrit, Sirawan Kamavichanurat, Wasan Joopor, Worawat Wattanathana, Chutikan Nakornkhet, Pimpa Hormnirun. Aluminium complexes of phenoxy-azo ligands in the catalysis of rac -lactide polymerisation. Dalton Transactions 2024, 53 (33) , 13854-13870. https://doi.org/10.1039/D4DT01758G
    6. Hao‐Yu Chung, Cian‐Fu Li, Ming‐Tsz Chen, Chi‐Tien Chen. Five‐ or six‐membered aluminum metallocyclic complexes containing N , N bidentate oxazolinyl‐indolate chelate ring: Synthesis, structural, and catalytic studies. Applied Organometallic Chemistry 2024, 36 https://doi.org/10.1002/aoc.7655
    7. Anirban Das, Nicholas B. Kingsley, Kristin Kirschbaum, Mark R. Mason. Bidentate and tridentate coordination modes of bis(3-methylindolyl)-2-(1-methylimidazolyl)methane in complexes of aluminum and gallium. Journal of Organometallic Chemistry 2023, 984 , 122554. https://doi.org/10.1016/j.jorganchem.2022.122554
    8. Chi-Tien Chen, Zi-Ling Lai. Aluminium complexes containing indolyl-phenolate ligands as catalysts for ring-opening polymerization of cyclic esters. RSC Advances 2022, 12 (43) , 28052-28058. https://doi.org/10.1039/D2RA05112E
    9. Federica Santulli, Giuseppe Gravina, Marina Lamberti, Consiglia Tedesco, Mina Mazzeo. Zinc and magnesium catalysts for the synthesis for PLA and its degradation: Clues for catalyst design. Molecular Catalysis 2022, 528 , 112480. https://doi.org/10.1016/j.mcat.2022.112480
    10. Qiuhong Song, Hongbo Tong, Meisu Zhou. Five-coordination aluminum complexes: Synthesis, crystal structures and utilization for the construction of substituted guanidines. Polyhedron 2022, 213 , 115619. https://doi.org/10.1016/j.poly.2021.115619
    11. Hussnain Sajjad, Emily A. Prebihalo, William B. Tolman, Theresa M. Reineke. Ring opening polymerization of β-acetoxy-δ-methylvalerolactone, a triacetic acid lactone derivative. Polymer Chemistry 2021, 12 (46) , 6724-6730. https://doi.org/10.1039/D1PY00561H
    12. Karunanidhi Murali, Luana A. Machado, Renato L. Carvalho, Leandro F. Pedrosa, Rishav Mukherjee, Eufrânio N. Da Silva Júnior, Debabrata Maiti. Decoding Directing Groups and Their Pivotal Role in C−H Activation. Chemistry – A European Journal 2021, 27 (49) , 12453-12508. https://doi.org/10.1002/chem.202101004
    13. Cristina Ruiz Martínez, Juana M. Pérez, Francisco M. Arrabal-Campos, María Batuecas, Manuel A. Ortuño, Ignacio Fernández. Cyclic polylactide synthesis initiated by a lithium anthraquinoid: understanding the selectivity through DFT and diffusion NMR. Polymer Chemistry 2021, 12 (28) , 4083-4092. https://doi.org/10.1039/D1PY00547B
    14. Massimo Christian D'Alterio, Claudio De Rosa, Giovanni Talarico. Syndiotactic PLA from meso -LA polymerization at the Al-chiral complex: a probe of DFT mechanistic insights. Chemical Communications 2021, 57 (13) , 1611-1614. https://doi.org/10.1039/D0CC07787A
    15. Yanay Popowski, Juan J. Moreno, Asa W. Nichols, Shelby L. Hooe, Caitlin J. Bouchey, Nigam P. Rath, Charles W. Machan, William B. Tolman. Mechanistic insight into initiation and regioselectivity in the copolymerization of epoxides and anhydrides by Al complexes. Chemical Communications 2020, 56 (90) , 14027-14030. https://doi.org/10.1039/D0CC05652A
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    Macromolecules

    Cite this: Macromolecules 2020, 53, 5, 1809–1818
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.0c00092
    Published February 18, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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