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

Anna M. Luke; Appie Peterson; Sina Chiniforoush; Mukunda Mandal; Yanay Popowski; Hussnain Sajjad; Caitlin J. Bouchey; Dimitar Y. Shopov; Brendan J. Graziano; Letitia J. Yao; Christopher J. Cramer; Theresa M. Reineke; William B. Tolman

doi:10.1021/acs.macromol.0c00092

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

Anna M. Luke, Appie Peterson, Sina Chiniforoush, Mukunda Mandal, Yanay Popowski, Hussnain Sajjad, Caitlin J. Bouchey, Dimitar Y. Shopov, Brendan J. Graziano, Letitia J. Yao, Christopher J. Cramer, Theresa M. Reineke, William B. Tolman

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13 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	1809-1818
Number of pages	10
Journal	Macromolecules
Volume	53
Issue number	5
DOIs	https://doi.org/10.1021/acs.macromol.0c00092
State	Published - Mar 10 2020

Bibliographical note

Funding Information:
This work was supported by the NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation, CHE-1901635. X-ray diffraction data were collected using diffractometers acquired through NSF-MRI Award No. CHE-1229400 (University of Minnesota) or 1827756 (Washington University in St. Louis).

Funding Information:
This work was supported by the NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation, CHE-1901635. X-ray diffraction data were collected using diffractometers acquired through NSF-MRI Award No. CHE-1229400 (University of Minnesota) or 1827756 (Washington University in St. Louis).

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Copyright © 2020 American Chemical Society.

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Luke, A. M., Peterson, A., Chiniforoush, S., Mandal, M., Popowski, Y., Sajjad, H., Bouchey, C. J., Shopov, D. Y., Graziano, B. J., Yao, L. J., Cramer, C. J., Reineke, T. M., & Tolman, W. B. (2020). Mechanism of Initiation Stereocontrol in Polymerization of rac-Lactide by Aluminum Complexes Supported by Indolide-Imine Ligands. Macromolecules, 53(5), 1809-1818. https://doi.org/10.1021/acs.macromol.0c00092

Luke, AM, Peterson, A, Chiniforoush, S, Mandal, M, Popowski, Y, Sajjad, H, Bouchey, CJ, Shopov, DY, Graziano, BJ, Yao, LJ, Cramer, CJ , Reineke, TM & Tolman, WB 2020, 'Mechanism of Initiation Stereocontrol in Polymerization of rac-Lactide by Aluminum Complexes Supported by Indolide-Imine Ligands', Macromolecules, vol. 53, no. 5, pp. 1809-1818. https://doi.org/10.1021/acs.macromol.0c00092

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title = "Mechanism of Initiation Stereocontrol in Polymerization of rac-Lactide by Aluminum Complexes Supported by Indolide-Imine Ligands",

abstract = "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.",

author = "Luke, {Anna M.} and Appie Peterson and Sina Chiniforoush and Mukunda Mandal and Yanay Popowski and Hussnain Sajjad and Bouchey, {Caitlin J.} and Shopov, {Dimitar Y.} and Graziano, {Brendan J.} and Yao, {Letitia J.} and Cramer, {Christopher J.} and Reineke, {Theresa M.} and Tolman, {William B.}",

note = "Funding Information: This work was supported by the NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation, CHE-1901635. X-ray diffraction data were collected using diffractometers acquired through NSF-MRI Award No. CHE-1229400 (University of Minnesota) or 1827756 (Washington University in St. Louis). Funding Information: This work was supported by the NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation, CHE-1901635. X-ray diffraction data were collected using diffractometers acquired through NSF-MRI Award No. CHE-1229400 (University of Minnesota) or 1827756 (Washington University in St. Louis). Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

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AU - Luke, Anna M.

AU - Peterson, Appie

AU - Chiniforoush, Sina

AU - Mandal, Mukunda

AU - Popowski, Yanay

AU - Sajjad, Hussnain

AU - Bouchey, Caitlin J.

AU - Shopov, Dimitar Y.

AU - Graziano, Brendan J.

AU - Yao, Letitia J.

AU - Cramer, Christopher J.

AU - Reineke, Theresa M.

AU - Tolman, William B.

N1 - Funding Information: This work was supported by the NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation, CHE-1901635. X-ray diffraction data were collected using diffractometers acquired through NSF-MRI Award No. CHE-1229400 (University of Minnesota) or 1827756 (Washington University in St. Louis). Funding Information: This work was supported by the NSF Center for Sustainable Polymers, a NSF Center for Chemical Innovation, CHE-1901635. X-ray diffraction data were collected using diffractometers acquired through NSF-MRI Award No. CHE-1229400 (University of Minnesota) or 1827756 (Washington University in St. Louis). Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/3/10

Y1 - 2020/3/10

N2 - 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.

AB - 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.

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

Abstract

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