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Ring-opening polymerization of ε-caprolactone catalysed by (pyridyl)benzoazole Zn(II) and Cu(II) complexes

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Abstract

This paper describes the synthesis of (pyridyl)benzoazole Zn(II) and Cu(II) complexes and their applications as catalysts in ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). Reactions of 2-(3-pyridyl)-1H-benzimidazole (L1), 2-(2-pyridyl)-1H-benzothiazole (L2) and 2-(2-pyridyl)-1H-benzimidazole (L3) with Zn(II) and Cu(II) acetates produced the corresponding complexes; [Zn2(L1)2(OAc)4)] (1), [Cu2(L1)2(OAc)4] (2), [Zn(L2)(OAc)2)] (3), [Zn(L3)(OAc)2)] (4) and [Cu(L3), (OAc)2)] (5). Molecular structures of complexes 2 and 5a revealed that while L1 adopts a monodentate binding mode, through the pyridyl nitrogen atom, L3 exhibits a bidentate coordination mode. All the complexes formed active catalysts in the ROP of ε-CL to afford moderate molecular weight polymers. The kinetics of the ROP reactions of ε-CL were pseudo-first-order with respect to monomer and catalysts.

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Acknowledgments

The authors would like to thank the University of KwaZulu-Natal for financial support.

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Authors and Affiliations

  1. School of Chemistry and Physics, University of KwaZulu-Natal, Pietermaritzburg Campus, Private Bag X01, Scottsville, 3209, South Africa

    Thembisile P. Zaca, Stephen O. Ojwach & Matthew P. Akerman

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  1. Thembisile P. Zaca
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  2. Stephen O. Ojwach
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  3. Matthew P. Akerman
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Corresponding author

Correspondence to Stephen O. Ojwach.

Electronic supplementary material

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11243_2016_66_MOESM1_ESM.docx

Supplementary Figures S1–S3 represent 1H NMR, ESI–MS spectra and crystal packing of complexes 4, 5 and 2, respectively. Figures S4 represents plots of ln[CL]0/[CL] t versus time versus time for catalysts 1–5, while Figure S5 depicts a plot of ln[CL]0/[CL] t versus time at different catalyst concentrations using 1. Typical GPC chromatogram of PCL sample is given in Figure S6, while ESI mass and 1H NMR spectra of the polymers are given in Figures S7 and S8. CCDC numbers 1404899 and 1404900 contain the supplementary crystallographic data for compounds 2 and 5a, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. (DOCX 1003 kb)

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Zaca, T.P., Ojwach, S.O. & Akerman, M.P. Ring-opening polymerization of ε-caprolactone catalysed by (pyridyl)benzoazole Zn(II) and Cu(II) complexes. Transit Met Chem 41, 663–673 (2016). https://doi.org/10.1007/s11243-016-0066-z

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  • DOI: https://doi.org/10.1007/s11243-016-0066-z

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