Zirconium vs aluminum salalen initiators for the production of biopolymers

Sarah M. Kirk; Gabriele Kociok-Kohn; Matthew D. Jones

doi:10.1021/acs.organomet.6b00718

Zirconium vs aluminum salalen initiators for the production of biopolymers

Sarah M. Kirk, Gabriele Kociok-Kohn, Matthew D. Jones

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Abstract

Herein we report the synthesis and full characterization (NMR and solid-state structures) for a series of Zr(IV), Hf(IV), and Al(III) salalen complexes, together with salen bimetallic counterparts. With the salalen ligand, 1H₂, monometallic complexes were observed in solution and solid state. Complex Zr(1)(OⁱPr)₂ was able to produce isotactic polylactide (PLA) from rac-lactide (P_m up to 0.85) in solution at 50 °C; in the melt (130 °C) this reduced to ca. 0.75. Al(1)Me was significantly less active and produced PLA with only a very modest isotactic enchainment (P_m ≈ 0.6). Zr(1)(OⁱPr)₂ was also able to produce copolymers with lactide and ϵ-caprolactone, producing copolymers of a "blocky" nature.

Original language	English
Pages (from-to)	3837-3843
Number of pages	7
Journal	Organometallics
Volume	35
Issue number	22
DOIs	https://doi.org/10.1021/acs.organomet.6b00718
Publication status	Published - 28 Nov 2016

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10.1021/acs.organomet.6b00718

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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.6b00718
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Cite this

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title = "Zirconium vs aluminum salalen initiators for the production of biopolymers",

abstract = "Herein we report the synthesis and full characterization (NMR and solid-state structures) for a series of Zr(IV), Hf(IV), and Al(III) salalen complexes, together with salen bimetallic counterparts. With the salalen ligand, 1H2, monometallic complexes were observed in solution and solid state. Complex Zr(1)(OiPr)2 was able to produce isotactic polylactide (PLA) from rac-lactide (Pm up to 0.85) in solution at 50 °C; in the melt (130 °C) this reduced to ca. 0.75. Al(1)Me was significantly less active and produced PLA with only a very modest isotactic enchainment (Pm ≈ 0.6). Zr(1)(OiPr)2 was also able to produce copolymers with lactide and ϵ-caprolactone, producing copolymers of a {"}blocky{"} nature.",

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AU - Kirk, Sarah M.

AU - Kociok-Kohn, Gabriele

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N2 - Herein we report the synthesis and full characterization (NMR and solid-state structures) for a series of Zr(IV), Hf(IV), and Al(III) salalen complexes, together with salen bimetallic counterparts. With the salalen ligand, 1H2, monometallic complexes were observed in solution and solid state. Complex Zr(1)(OiPr)2 was able to produce isotactic polylactide (PLA) from rac-lactide (Pm up to 0.85) in solution at 50 °C; in the melt (130 °C) this reduced to ca. 0.75. Al(1)Me was significantly less active and produced PLA with only a very modest isotactic enchainment (Pm ≈ 0.6). Zr(1)(OiPr)2 was also able to produce copolymers with lactide and ϵ-caprolactone, producing copolymers of a "blocky" nature.

AB - Herein we report the synthesis and full characterization (NMR and solid-state structures) for a series of Zr(IV), Hf(IV), and Al(III) salalen complexes, together with salen bimetallic counterparts. With the salalen ligand, 1H2, monometallic complexes were observed in solution and solid state. Complex Zr(1)(OiPr)2 was able to produce isotactic polylactide (PLA) from rac-lactide (Pm up to 0.85) in solution at 50 °C; in the melt (130 °C) this reduced to ca. 0.75. Al(1)Me was significantly less active and produced PLA with only a very modest isotactic enchainment (Pm ≈ 0.6). Zr(1)(OiPr)2 was also able to produce copolymers with lactide and ϵ-caprolactone, producing copolymers of a "blocky" nature.

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Zirconium vs aluminum salalen initiators for the production of biopolymers

Abstract

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HPLC System

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Zirconium vs aluminum salalen initiators for the production of biopolymers

Abstract

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Dual source (Cu and Mo) Single Crystal Diffractometer (SuperNova)

HPLC System

MC2- X-ray diffraction (XRD)

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