Ring Opening Polymerization of <italic style="font-style: italic">ω</italic>-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky <italic style="font-style: italic">α</italic>-Diimine Ligands

Li-Jia Liu; Wen-Peng Zhao; Li-Shuang Ma; Chun-Yu Zhang; Feng Wang; Xue-Quan Zhang; Heng Liu

doi:10.1007/s10118-025-3303-0

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Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands

RESEARCH ARTICLE | Updated：2025-07-14

- Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands
- Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands
- 高分子科学（英文） 2025年43卷第4期页码：640-654
- Affiliations：
  
  a.Shandong Provincial College Laboratory of Rubber Material and Engineering/Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
  b.College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
- Author bio：
  
  zwp@qust.edu.cn (W.P.Z.)
  fengwang@qust.edu.cn (F.W.)
  hengliu@qust.edu.cn (H.L.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 21901020 and 22003076), China Postdoctoral Science Foundation (No. 2021M701818), and Shandong Provincial Natural Science Foundation (No. ZR2022QE237), and the Qingdao Postdoctoral Applied Research Project. H. Liu sincerely acknowledges financial support from the Taishan Scholars Program (No. tsqn202211165).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3303-0.
- DOI：10.1007/s10118-025-3303-0
  中图分类号：
- 收稿：2024-10-31，
  
  修回：2024-12-23，
  
  录用：2024-12-29，
  
  网络首发：2025-03-13，
  
  纸质出版：2025-04-01
- Accepted：
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Liu, L. J.; Zhao, W. P.; Ma, L. S.; Zhang, C. Y.; Wang, F.; Zhang, X. Q.; Liu, H. Ring opening polymerization of ω-pentadecalactone by weakly oxophilic Fe(II)-based catalytic systems bearing bulky α-diimine ligands. Chinese J. Polym. Sci. 2025, 43, 640–654

Li-Jia Liu, Wen-Peng Zhao, Li-Shuang Ma, et al. Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands[J]. Chinese Journal of Polymer Science, 2025, 43(4): 640-654. DOI: 10.1007/s10118-025-3303-0.
Liu, L. J.; Zhao, W. P.; Ma, L. S.; Zhang, C. Y.; Wang, F.; Zhang, X. Q.; Liu, H. Ring opening polymerization of ω-pentadecalactone by weakly oxophilic Fe(II)-based catalytic systems bearing bulky α-diimine ligands. Chinese J. Polym. Sci. 2025, 43, 640–654 DOI： 10.1007/s10118-025-3303-0.

Li-Jia Liu, Wen-Peng Zhao, Li-Shuang Ma, et al. Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands[J]. Chinese Journal of Polymer Science, 2025, 43(4): 640-654. DOI: 10.1007/s10118-025-3303-0. DOI：

摘要

A family of bulky

-diimine Fe(II) complexes were reported to catalyze ring opening polymerization (ROP) of a large ring-sized macrolactone

-pentadecalactone (PDL)

with high catalytic efficiencies. With the aid of bulky nature of the ligands

transesterification reactions could be significantly suppressed

allowing the polymerization proceed in a living-like manner.

Abstract

High catalytic efficiencies in ring opening polymerization (ROP) of a large ring-sized macrolactone

-pentadecalactone (PDL)

by using transition metal Fe(II)-based catalysts were achieved for the first time in this study. Benefited from the bulky nature of the ligated

-diimine ligands

as evidenced from single-crystal structures

as well as the weakly oxophilic nature of the metal centers

chain transesterification reactions could be partially suppressed

allowing the polymerization proceed in a living-like and semi-controllable manner

i.e.

good linear dependence of propagation rates on catalyst concentration and PDL concentration as observed in the detailed kinetics studies. The whole polymerization proceeds

via

a “coordination-insertion” mechanism

and with the aid of density functional theory (DFT) calculation studies

a “slow insertion → fast elimination” manner was demonstrated for the monomer propagation step

suggesting the insertion of Fe-OR into the carbonyl group C＝O as the rate-determining step. The present catalytic system also showed fast chain transfer reactions to alcohol compounds

affording quasi-immortal characteristics. DFT calculations showed that such a transfer reaction only required an energy barrier of 6.4 kcal/mol

performing a good consistency with the fast

chain transfer rates.

关键词

Keywords

references

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Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands

Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands

DOI：10.1007/s10118-025-3303-0

摘要

Abstract

关键词

Keywords

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